Environmental Isotopes in theHydrological Cycle

Principles and Applications

Vol. 1
Water Resources Programme

Atoms for Peace

International Atomic Energy Agency and United Nations Educational, Scientific and Cultural Organization
Atoms for Peace

(reprinted with minor corrections)

Environmental Isotopes in theHydrological Cycle

Principles and Applications

International Atomic Energy Agency and United Nations Educational, Scientific and Cultural Organization (reprinted with minor corrections)

FOREWORD

The increasing demand for water in many regions of the world has been generally translated into intensive and too often unsustainable, exploitation of water resources. In many instances, natural and man-made changes have profoundly affected the local hydrological cycle. Under these circumstances, more detailed information is often required for a more precise assessment of water resources and for the adoption of sustainable management practices. Environmental isotopes have been extensively used during the last decades to address key aspects of the water cycle, such as the study of the origin, dynamics and interconnections of for example, groundwater, surface water and the atmosphere. The use of environmental isotopes as tracers of the water molecule has been extended beyond the classical applications of Isotope Hydrology and today, a growing number of other scientific disciplines, ranging from atmospheric circulation to palaeoclimatology or ecology have incorporated isotopes as powerful tracers to better characterize systems and processes. Expanding the use of isotope hydrology tools to conduct hydrological studies relies on the adequate training of scientists and technicians in

Member States and access to information. The IAEA has played a key role over the years in capacity building, especially with regard to conducting individualized and group trainings on how to use isotopes to improve water resources management. This publication is a reprint of a six-volume joint IAEA-UNESCO document released in 2001 as part of the IHP-V International Hydrological Programme (Technical Documents in Hydrology, No. 39). This document was originally edited by W.G Mook and has been extensively used during the last decade in training courses, seminars and workshops, by the IAEA and others, dealing with teaching the basic principles on the use of environmental isotopes in hydrology and related fields. The publication has been a successful technical reference as a training tool, and has been translated into French and Spanish. It has been distributed as hard copy and electronic files in training packages and through the IAEA web page. Now it is made available in the form of IAEA Training Course Series in a single volume. The IAEA officer responsible for this publication is Pradeep Aggarwal of the Division of Physical and Chemical Sciences.

PrEface

Theavailability of freshwater is one of thegreat issues facing mankind today in some ways thegreatest, because problems associated with it affect thelives of many millions of people. It has consequently attracted awide scale international attention of UN Agencies and related international/regional governmental and non-governmental organisations. Therapid growth of population coupled to steady increase in water requirements for agricultural and industrial development have imposed severe stress on theavailable freshwater resources in terms of both thequantity and quality, requiring consistent and careful assessment and management of water resources for their sustainable development. More and better water can not be acquired without thecontinuation and extension of hydrological research. In this respect has thedevelopment and practical implementation of isotope methodologies in water resources assessment and management been part of theIAEAs programme in nuclear applications over thelast four decades. Isotope studies applied to awide spectrum of hydrological problems related to both surface and groundwater resources as well as environmental studies in hydro-ecological systems are presently an established scientific discipline, often referred to as Isotope Hydrology. TheIAEA contributed to this development through direct support to research and training, and to theverification of isotope methodologies through field projects implemented in Member States. Theworld-wide programme of theInternational Hydrological Decade (19651974) and thesubsequent long-term International Hydrological Programme (IHP) of UNESCO have been an essential part of thewell recognised international frameworks for scientific research, education and training in the field of hydrology. TheInternational Atomic Energy Agency (IAEA) and UNESCO have established aclose co-operation within theframework of both theearlier IHD and theongoing IHP in thespecific aspects of scientific and methodological developments related to water resources that are of mutual interest to theprogrammes of both organisations. Thefirst benchmark publication on isotope hydrology entitled Guidebook on Nuclear Techniques in

Hydrology was realised in 1983 through theactivity of thejoint IAEA/UNESCO Working Group on Nuclear Techniques established within theframework of IHP, and it has been widely used as practical guidance material in this specific field. In view of thefact that theIHPs objectives include also amulti-disciplinary approach to theassessment and rational management of water resources and taking note of theadvances made in isotope hydrology, theIAEA and UNESCO have initiated ajoint activity in preparation of aseries of six up-to-date textbooks, covering theentire field of hydrological applications of natural isotopes (environmental isotopes) to theoverall domain of water resources and related environmental studies. Themain aim of this series is to provide acomprehensive review of basic theoretical concepts and principles of isotope hydrology methodologies and their practical applications with some illustrative examples. Thevolumes are designed to be self-sufficient reference material for scientists and engineers involved in research and/or practical applications of isotope hydrology as an integral part of theinvestigations related to water resources assessment, development and management. Furthermore, they are also expected to serve as Teaching Material or text books to be used in universities and teaching institutions for incorporating thestudy of isotopes in water in general into thecurriculum of theearth sciences. Additionally the contents can fulfil the need for basic knowledge in other disciplines of theEarth Sciences dealing with water in general. These six volumes have been prepared through efforts and contributions of anumber of scientists involved in this specific field as cited in each volume, under theguidance and co-ordination of themain author/co-ordinating editor designated for each volume. W. G. Mook (Netherlands), J.Gat (Israel), K.Rozanski (Poland), W. Stichler (Germany), M.Geyh (Germany), K. P. Seiler (Germany) and Y.Yurtsever (IAEA, Vienna) were involved as themain author/co-ordinating editors in preparation of these six volumes, respectively. Final editorial work on all volumes aiming to achieve consistency in thecontents and layout throughout thewhole series was undertaken by W.G.Mook (Netherlands).

Mr.Y. Yurtsever, Staff Member of the Isotope Hydrology Section of the IAEA; and Ms.A.Aureli, Programme Specialist, Division of Water Sciences of UNESCO, were theScientific Officers in charge of co-ordination and providing scientific secretariat to the various meetings and activities that were undertaken throughout thepreparation of these publications. TheIAEA and UNESCO thank all those who have contributed to thepreparation of these vol-

umes and fully acknowledge theefforts and achievements of themain authors and co-ordinating editors. It is hoped that these six volumes will contribute to wider scale applications of isotope methodologies for improved assessment and management of water resources, facilitate incorporation of isotope hydrology into thecurricula of teaching and education in water sciences and also foster further developments in this specific field.

Paris / Vienna, March 2000

TABLE OF CONTENTS
VOLUME I: INTRODUCTION Theory, methods, review The Global Cycle of water...................................................................................................... 1 ATOMIC SYSTEMATICS AND NUCLEAR STRUCTURe............................................................... 19 Abundance and fractionation of stable isotopes .................................................. 23 ABUNDANCE VARIATIONS by NATURAL PROCESSEs............................................................. 33 rADIOnuclide DECAY and production............................................................................... 43 EQUATIONS OF RADIOACTIVE DECAY AND GROWTH............................................................. 49 natural abundance of thestable isotopes of C, O and H..................................... 55 NATURAL ABUNDANCE OF RADIOACTIVE ISOTOPES of C and H...................................... 75 CHEMISTRY OF CARBONIC ACID IN WATER............................................................................... 87 Water sampling and laboratory treatment............................................................... 99 measuring techniques............................................................................................................ 107 natural isotopes of elements other than h, c, o.................................................... 127 errors, means and fits............................................................................................................ 145 VOLUME II: Atmospheric water TheAtmosphere........................................................................................................................... 171 ISOTOPE METHODOLOGY............................................................................................................. 175 Stable isotope processes in thewater cycle............................................................ 181 Observed isotope effects in precipitation................................................................... 197 TRITIUM IN theatmosphere.................................................................................................... 209 Isotopes De CO2 et O2 Atmospheriques.............................................................................. 217 VOLUME III: Surface Water BASIC CONCEPTS AND MODELS.................................................................................................. 243 Rivers................................................................................................................................................ 249 Estuaries and theSea.............................................................................................................. 273 LAKES AND RESERVOIRS.............................................................................................................. 279 RESPONSE OF SURFACE WATER SYSTEMS TO CLIMATIC CHANGES.................................. 299

VOLUME IV: groundwater saturated and unsaturated zone Hydrogeology and aquifer characteristics........................................................... 317 Tracers and transport.......................................................................................................... 327 Geohydraulic aspects............................................................................................................ 333 WaterRock interactions..................................................................................................... 343 Applications to low-Temperature systems................................................................. 349 Applications tO high-Temperature systems................................................................ 389 Planning and performance of multiple isotope studies.................................... 409 References..................................................................................................................................... 413 VOLUME V: Mans impact on groundwater systems pOLLUTION SUSCEPTIBILITY OF AQUIFERS and pollution assessment................. 431 GROUNDWATER EXPLOITATION AND OVEREXPLOITATION................................................ 443 irrigation and theimpact on groundwater quality............................................ 455 IMPACT OF URBANISATION ON GROUNDWATER.................................................................... 463 IMPACT OF LAND USE ON GROUNDWATER QUALITY........................................................... 469 SAMPLING OF WATER QUANTITIES, METHODS, points of ATTENTION .................... 477 Outlook to further applications.................................................................................... 483 VOLUME VI: modelling modelling INTRODUCTION....................................................................................................... 495 LUMPED PARAMETER MODELS................................................................................................... 497 COMPARTMENTAL MODEL APPROACHES TO GROUNDWATER FLOW SIMULATION...... 517 USE OF NUMERICAL MODELS TO SIMULATE GROUNDWATER FLOW AND TRANSPORT............................................................................................................................... 541

Ar H C He Kr

ENVIRONMENTAL ISOTOPES in the HYDROLOGICAL CYCLE

H O

C N S He Ar

VOLUME I INTRODUCTION Theory, methods, review

Willem G. Mook Centre for Isotope Research, Groningen

Contribution de J.J.de Vries, Free University, Amsterdam Titre original en Anglais: Environmental Isotopes in thehydrological cycle. Principles and applications IHP-V Technical Documents in Hydrology, N 39. UNESCO IAEA 2001

Preface to volume I
The first volume in the series of textbooks on theenvironmental isotopes in thehydrological cycle is theresult of are-orientation and in part extension of thelecture notes I used during theyears I was teaching thehydrology students of theFree University of Amsterdam an annual course in Isotope Hydrology. During these years my colleague and friend, Joe Pearson, and I set ourselves to publish thelecture notes, but did not find thetime for theaccomplishment of this task. Now I have come to realise how much he taught me and I gratefully acknowledge those days. The need for international agreement on definitions and theuse of symbols can not be sufficiently emphasised. In this introductory volume I have aimed at consistency as well as mathematical and physical correctness. However, it is unavoidable that, for historical reasons, thesame consistency could not be continued in all subsequent volumes. Thesecond important aim of this volume has been to present no equations dealing with isotopes without theproper and understandable mathematical derivation. After an introductory chapter on thehydrological cycle, this volume contains theprinciples of radioactivity and of theisotope effects for stable isotopes. Theelements of hydrogen, carbon and oxygen are being treated in detail, as they form theheart of isotopic applications in thewater cycle. Thecontribution of theother isotopes is discussed less extensively in this volume. Concrete isotopic applications in hydrology, here only touched at in an illustrative manner, have become greatly expanded by my colleagues in thenext volumes. We felt that it is preferable that subjects of more general interest to theother volumes, such as theaqueous chemistry of inorganic carbon, thetreatment of water samples in thefield and in thelaboratory, thetechniques of isotopic analyses, thestatistical treatment of data, should be treated in thefirst volume. This series of 6 volumes are meant to be textbooks. This leads to certain requirements different from theexisting handbooks. Especially in this introductory volume I have kept thenumber of references to literature minimal, in favour of thereadability of thetext. I owe much gratitude to theformer co-workers of my lab for their assistance in reading themanuscript, making many corrections, pointing out subjects that were failing and explanations that could not well be understood, in short for their continuing hospitality. To my colleagues co-authors of this series I want to express my appreciation for our highly stimulating and pleasant co-operation

Groningen, 29 February2000 Willem G Mook

TABLE OF CONTENTS OF volume I

1. The Global Cycle of water............................................................................................... 1 1.1. Introduction.......................................................................................................................... 1 1.2. The Hydrosphere.................................................................................................................. 1 1.2.1. Origin of water on Earth........................................................................................ 1 1.2.2. The hydro-tectonic cycle....................................................................................... 2 1.2.3. Distribution of water over thevarious reservoirs.................................................. 3 1.3. Theglobal water budget....................................................................................................... 4 1.4. Components of thehydrological cycle................................................................................. 5 1.4.1. Evaporation ........................................................................................................... 5 1.4.2. Precipitation and atmospheric circulation.............................................................. 6 1.4.3. Discharge from thecontinents............................................................................... 8 1.4.4. Groundwater ......................................................................................................... 9 1.4.5. Continental water surplus and water use............................................................. 12 1.5. Thehydrosphere and global change................................................................................... 12 1.5.1. Climatic change................................................................................................... 12 1.5.2. Thehuman factor................................................................................................. 14 1.5.2.1. Irrigation............................................................................................. 15 1.5.2.2. Wetland drainage................................................................................ 15 1.1.1.1 Ground cover damage......................................................................... 15 1.5.2.3. Deforestation...................................................................................... 16 1.5.2.4. Interbasin diversion............................................................................ 16 1.5.2.5. Streamflow management.................................................................... 16 1.5.2.6. Land use changes................................................................................ 16 1.6. Isotopes in the hydrological cycle..................................................................................... 16 2. ATOMIC SYSTEMATICS AND NUCLEAR STRUCTURe....................................................... 19 2.1. 2.2. 2.3. 2.4. 3. 3.1. 3.2. 3.3. 3.4. 3.5. 3.6. 3.7. 4. 4.1. 4.2. Atomic structure and theperiodic table of theelements.................................................... 19 Structure of theatomic nucleus.......................................................................................... 19 Stable and radioactive isotopes.......................................................................................... 20 Mass and energy................................................................................................................. 20 Isotope ratios and concentrations....................................................................................... 23 Isotope fractionation........................................................................................................... 23 Kinetic and equilibrium isotope fractionation.................................................................... 25 Theoretical background of equilibrium fractionation........................................................ 27 Fractionation by diffusion.................................................................................................. 30 Relation between atomic and molecular isotope ratios...................................................... 30 Relation between fractionations for three isotopic molecules........................................... 31 Use of values and isotope references.............................................................................. 33 Tracer concentration, amount of tracer.............................................................................. 34

Abundance and fractionation of stable isotopes .......................................... 23

ABUNDANCE VARIATIONS by NATURAL PROCESSEs...................................................... 33

4.3.

4.4.

Mixing of reservoirs with different isotopic composition.................................................. 35 4.3.1. Mixing of reservoirs of thesame compound....................................................... 35 4.3.1.1. Isotopic dilution analysis.................................................................... 36 4.3.2. Mixing of reservoirs of different compounds...................................................... 37 Isotopic changes in Rayleigh processes............................................................................. 37 4.4.1. Reservoir with one sink....................................................................................... 37 4.4.2. Reservoir with two sinks...................................................................................... 38 4.4.3. Reservoir with one source and one sink, as afunction of time........................... 38 4.4.4. Reservoir with one source and one sink, s afunction of mass............................ 40 4.4.5. Reservoir with two sources and two sinks, with and without fractionation........ 40 Nuclear instability.............................................................................................................. 43 Nuclear decay and radiation............................................................................................... 43 5.2.1. Negatron () decay............................................................................................. 43 5.2.2. Positron (+) decay............................................................................................... 43 5.2.3. Electron capture (EC).......................................................................................... 44 5.2.4. Alpha () decay................................................................................................... 45 5.2.5. Spontaneous and induced fission, neutron emission............................................ 45 Recoil by radioactive decay............................................................................................... 45 Nuclear reactions................................................................................................................ 45 5.4.1. Natural production............................................................................................... 46 5.4.2. Anthropogenic releases of radionuclides............................................................. 46

5. rADIOnuclide DECAY and production........................................................................ 43 5.1. 5.2.

5.3. 5.4.

6.

EQUATIONS OF RADIOACTIVE DECAY AND GROWTH..................................................... 49 6.1. Law of radioactive decay................................................................................................... 49 6.2. Half-life and mean life....................................................................................................... 49 6.3. Activity, specific activity and radionuclide concentration................................................. 50 6.4. Mixture of independent radioactivities.............................................................................. 50 6.5. Branching decay................................................................................................................. 50 6.6. Radioactive decay series.................................................................................................... 51 6.6.1. Secular equilibrium.............................................................................................. 51 6.6.2. Transient equilibrium........................................................................................... 52 6.6.3. No-equilibrium..................................................................................................... 52 6.7. Accumulation of stable daughter product.......................................................................... 53 6.8. Radioactive growth............................................................................................................ 53

7. natural abundance of thestable isotopes of C, O and H.............................. 55 7.1. Table carbon isotopes......................................................................................................... 55 7.1.1. Thenatural abundance......................................................................................... 55 7.1.2. Carbon isotope fractionations.............................................................................. 55 7.1.3. Reporting 13C variations and the13C standard .................................................... 59 7.1.4. Survey of natural 13C variations........................................................................... 59 7.1.4.1. Atmospheric CO2 ............................................................................... 60 7.1.4.2. Seawater and marine carbonate.......................................................... 60 7.1.4.3. Vegetation and soil CO2 ..................................................................... 60

7.2.

7.3. 7.4.

7.5. 8. 8.1.

7.1.4.4. Fossil fuel........................................................................................... 60 7.1.4.5. Global carbon cycle............................................................................ 60 7.1.4.6. Groundwater and riverwater............................................................... 61 Stable oxygen isotopes....................................................................................................... 61 7.2.1. Thenatural abundance......................................................................................... 61 7.2.2. Oxygen isotope fractionations............................................................................. 62 7.2.3. Reporting 18O variations and the18O standards................................................... 63 7.2.4. Survey of natural 18O variations........................................................................... 66 7.2.4.1. Seawater............................................................................................. 66 7.2.4.2. Precipitation........................................................................................ 66 7.2.4.3. Surface water...................................................................................... 68 7.2.5. Climatic variations............................................................................................... 68 Relation between 13C and 18O variations in H2O, HCO!, and CO$................................... 68 Stable hydrogen isotopes.................................................................................................... 69 7.4.1. Thenatural abundance......................................................................................... 69 7.4.2. Hydrogen isotope fractionations.......................................................................... 70 7.4.3. Reporting 2H variations and the2H standard....................................................... 70 7.4.4. Survey of natural 2H variations............................................................................ 70 Relation between 2H and 18O variations in water................................................................ 70 Theradioactive carbon isotope.......................................................................................... 75 8.1.1. Origin of 14C, decay and half-life......................................................................... 75 8.1.2. Reporting 14C variations and the14C standard..................................................... 76 8.1.3. Survey of natural 14C variations........................................................................... 77 8.1.3.1. Atmospheric CO2 ............................................................................... 77 8.1.3.2. Vegetation and soils............................................................................ 78 8.1.3.3. Seawater and marine carbonate.......................................................... 78 8.1.3.4. Groundwater....................................................................................... 78 8.1.4. 14C age determination.......................................................................................... 79 8.1.5. Dating groundwater............................................................................................. 80 8.1.5.1. Dating groundwater with DIC............................................................ 80 8.1.5.2. Dating groundwater with DOC.......................................................... 81 Relation between 13C and 14C variations............................................................................ 82 Theradioactive hydrogen isotope...................................................................................... 82 8.3.1. Origin of 3H, decay and half-life.......................................................................... 82 8.3.2. Reporting 3H activities and the3H standard......................................................... 82 8.3.3. Survey of natural 3H variations............................................................................ 82 Comparison of 3H and 14C variations................................................................................. 83 8.4.1. Relation between 3H and 14C in theatmosphere.................................................. 83 8.4.2. Relation between 3H and 14C in groundwater...................................................... 84

NATURAL ABUNDANCE OF RADIOACTIVE ISOTOPES of C and H............................... 75

8.2. 8.3.

8.4.

9.

CHEMISTRY OF CARBONIC ACID IN WATER........................................................................ 87 9.1. Introduction........................................................................................................................ 87 9.2. Carbonic acid equilibria..................................................................................................... 87 9.3. Theequilibrium constants.................................................................................................. 88

9.4. 9.5.

9.3.1. Ideal solutions...................................................................................................... 89 9.3.2. Seawater............................................................................................................... 89 9.3.3. Brackish water..................................................................................................... 90 Carbonic acid concentrations............................................................................................. 90 Examples for open and closed systems.............................................................................. 93 9.5.1. Comparison of freshwater and seawater exposed to theatmosphere.................. 93 9.5.1.1. For freshwater..................................................................................... 94 9.5.1.2. For seawater........................................................................................ 94 9.5.2. System open for CO2 escape and CaCO3 formation............................................ 95 9.5.2.1. Starting conditions.............................................................................. 95 9.5.2.2. Escape of CO2 .................................................................................... 96 9.5.2.3. Precipitation of CaCO3 ...................................................................... 96 9.5.3. System exposed to CO2 in thepresence of Caco3 ............................................... 97 9.5.4. Closed system, mixing of freshwater and seawater............................................. 97

10. Water sampling and laboratory treatment........................................................ 99 10.1. Water sampling and storage............................................................................................... 99 10.1.1. Sampling bottles.................................................................................................. 99 10.1.2. General field practice........................................................................................... 99 10.1.3. Precipitation....................................................................................................... 100 10.1.4. Surface water..................................................................................................... 100 10.1.5. Unsaturated zone water...................................................................................... 100 10.1.6. Groundwater...................................................................................................... 100 10.1.7. Geothermal water............................................................................................... 101 10.2. Laboratory treatment of water samples............................................................................ 101 18 O/16O analysis of water............................................................................. 101 10.2.1. The 10.2.1.1. Equilibration with CO2 for mass spectrometric measurement......... 101 10.2.1.2. Other methods.................................................................................. 102 2 H/1H analysis of water............................................................................... 103 10.2.2. The 10.2.2.1. Reduction of water to H2 for mass spectrometric analysis............... 103 10.2.2.2. Other methods.................................................................................. 103 3 H analysis of water.................................................................................... 103 10.2.3. The 10.2.3.1. Water purification............................................................................. 103 10.2.3.2. 3H enrichment.................................................................................. 103 10.2.3.3. Preparation of gas for PGC of 3H..................................................... 104 14 C analysis of dissolved inorganic carbon................................................. 104 10.2.4. The 10.2.4.1. In thefield......................................................................................... 104 10.2.4.2. In thelabo0ratory............................................................................. 105 13 C/12C analysis of dissolved inorganic carbon........................................... 105 10.2.5. The 11. measuring techniques.................................................................................................... 107 11.1. Mass spectrometry for stable isotopes............................................................................. 107 11.1.1. Physical principle............................................................................................... 107 11.2. Reporting stable isotope Abundance ratios...................................................................... 108 11.2.1. Measurement of 2H/1H in H2 ............................................................................. 108 11.2.2. Measurement of 15N/14N in N2 ........................................................................... 109

11.2.3. Measurement of 13C/12C and 18O/16O in CO2 ..................................................... 109 11.2.3.1. Comparison with machine reference................................................ 109 11.2.4. Calibration......................................................................................................... 109 11.2.4.1. Isotopic corrections...........................................................................110 11.2.4.2. 18O correction for waterCO2 equilibration......................................111 11.2.4.3. Normalisation....................................................................................111 11.2.5. Measurement of 18O/16O and 17O/16 in O2 ...........................................................113 11.3. Radiometry for radioactive isotopes.................................................................................113 11.3.1. Gas counters........................................................................................................114 11.3.1.1. Ionisation chamber............................................................................114 11.3.1.2. Proportional counter..........................................................................114 11.3.1.3. Geiger Mller counter.......................................................................114 11.3.1.4. Counter operation..............................................................................115 11.3.2. Liquid scintillation spectrometer........................................................................116 11.3.2.1. Physical principle..............................................................................116 11.3.2.2. Counter operation..............................................................................116 11.4. Mass spectrometry for low-abundance isotopes...............................................................117 11.4.1. Principle and application of AMS.......................................................................117 11.5. Reporting 14C activities and concentrations......................................................................118 11.5.1. Thechoice of variables.......................................................................................118 11.5.2. Thestandardisation............................................................................................ 120 11.5.2.1. Thequestion of isotope fractionation............................................... 120 11.5.2.2. Thequestion of radioactive decay.................................................... 120 11.5.2.3. Definition of the14C standard activity.............................................. 120 11.5.3. Final definitions................................................................................................. 121 11.5.4. Special cases...................................................................................................... 121 11.5.4.1. Hydrology......................................................................................... 122 11.5.4.2. Oceanography and atmospheric research......................................... 122 11.5.4.3. Geochemistry.................................................................................... 123 11.5.4.4. Enhanced 14C radioactivity............................................................... 124 11.5.4.5. 14C ages............................................................................................ 124 11.5.5. Summary............................................................................................................ 124 12. natural isotopes of elements other than h, c, o............................................ 127 12.1. Helium.............................................................................................................................. 128 12.1.1. Origin and characteristics.................................................................................. 128 12.1.2. Experimental and technical aspects................................................................... 128 12.1.3. Sources of 3He.................................................................................................... 128 12.1.4. Natural abundance............................................................................................. 128 12.1.5. Applications....................................................................................................... 129 12.1.5.1. Principle of 3H/3He dating................................................................ 129 12.1.5.2. Mass spectrometric measurement of 3H through 3He....................... 129 12.2. Lithium............................................................................................................................. 129 12.2.1. Natural abundance............................................................................................. 129 12.2.2. Experimental and technical aspects................................................................... 129 12.2.3. Applications....................................................................................................... 130

INTRODUCTION

12.3. Beryllium.......................................................................................................................... 130 12.3.1. Origin and characteristics.................................................................................. 130 12.3.2. Experimental and technical aspects................................................................... 130 12.3.3. Natural abundance............................................................................................. 130 12.3.4. Applications....................................................................................................... 130 12.4. Boron................................................................................................................................ 130 12.4.1. Natural abundance............................................................................................. 130 12.4.2. Experimental and technical aspects................................................................... 131 12.4.3. Applications....................................................................................................... 131 12.5. Nitrogen............................................................................................................................ 131 12.5.1. Experimental and technical aspects................................................................... 131 12.5.2. Natural abundance and isotope fractionation..................................................... 131 12.5.3. Applications ...................................................................................................... 131 12.5.4. 18O/16O in nitrate................................................................................................. 131 12.6. Aluminium....................................................................................................................... 132 12.6.1. Origin and characteristics.................................................................................. 132 12.6.2. Experimental and technical aspects................................................................... 132 12.6.3. Natural abundance............................................................................................. 132 12.6.4. Applications....................................................................................................... 132 12.7. Silicon............................................................................................................................... 132 12.7.1. Origin and characteristics.................................................................................. 132 12.7.2. Natural abundance............................................................................................. 133 12.7.3. Experimental and technical aspects................................................................... 133 12.7.4. Applications....................................................................................................... 133 12.8. Sulphur............................................................................................................................. 133 12.8.1. Experimental and technical aspects................................................................... 133 12.8.2. Natural abundance............................................................................................. 134 12.8.3. Applications....................................................................................................... 134 12.9. Chlorine............................................................................................................................ 134 12.9.1. Radioactive 36Cl................................................................................................. 134 12.9.1.1. Origin and characteristics................................................................. 134 12.9.1.2. Experimental and technical aspects.................................................. 134 12.9.1.3. Abundance in nature......................................................................... 135 12.9.1.4. Applications...................................................................................... 135 12.9.2. Stable 35Cl and 37Cl............................................................................................ 135 12.9.2.1. Natural abundance and applications................................................. 135 12.9.2.2. Experimental and technical aspects.................................................. 136 12.10. Argon................................................................................................................................ 136 12.10.1. Origin and characteristics................................................................................. 136 12.10.2. Experimental and technical aspects.................................................................. 136 12.10.3. Natural abundance............................................................................................ 136 12.10.4. Applications...................................................................................................... 136 12.11. Krypton............................................................................................................................ 136 12.11.1. Origin and characteristics................................................................................. 136 12.11.2. Experimental and technical aspects.................................................................. 137

xviii

12.11.3. Natural abundance............................................................................................. 137 12.11.4. Applications....................................................................................................... 138 12.12. Iodine................................................................................................................................ 138 12.12.1. Origin and characteristics................................................................................. 138 12.12.2. Experimental and technical aspects.................................................................. 139 12.12.3. Natural abundance............................................................................................ 139 12.12.4. Applications...................................................................................................... 139 12.13. Decay series...................................................................................................................... 139 12.14. Theuranium series .......................................................................................................... 139 12.14.1. 238U/234U............................................................................................................. 139 12.14.2. 230Th 234U dating.............................................................................................. 140 12.14.3. 226Ra and 222Rn................................................................................................... 140 12.14.4. 210Pb................................................................................................................... 140 12.14.5. Experimental and technical aspects.................................................................. 141 12.15. Theactinium series........................................................................................................... 141 12.16. TheThorium series........................................................................................................... 142 13. errors, means and fits.................................................................................................... 145 13.1. Errors................................................................................................................................ 145 13.2. Precision and accuracy..................................................................................................... 145 13.2.1. Definitions.......................................................................................................... 145 13.2.2. Significant figures and digits.............................................................................. 145 13.2.3. uncertainties....................................................................................................... 146 13.3. Instrumental uncertainties................................................................................................ 147 13.3.1. Mean values....................................................................................................... 147 13.3.2. Distribution of data............................................................................................ 147 13.3.3. Standard deviation............................................................................................. 148 13.3.3.1. Precision of data............................................................................... 148 13.3.3.2. Precision of themean....................................................................... 148 13.4. Statistical uncertainties..................................................................................................... 149 13.5. error Propagation.............................................................................................................. 149 13.5.1. Standard deviation............................................................................................. 149 13.5.2. Weighted mean................................................................................................... 150 13.6. Least-squares fit................................................................................................................ 150 13.6.1. Fit to astraight line............................................................................................ 150 13.6.2. Fit to non-linear curves...................................................................................... 151 13.7. Chi-square test.................................................................................................................. 151 Symbols and units..................................................................................................................... 153 Literature...................................................................................................................................... 155 References..................................................................................................................................... 159

The Global Cycle of water

1. The Global Cycle of water

1.1. Introduction Theglobal hydrological cycle together with its driving force, solar radiation, forms thebasic resource for primary biological production. It provides thewater that is required for theassimilation of carbon and plays an important role in thesupply of nutrients and their transport. Moreover, thehydrological cycle is responsible for themoderate and favourable temperature conditions prevailing on Earth through its linkage with theglobal atmospheric cycle. Thehydrosphere is theinterconnection between thebiosphere, theatmosphere and thelithosphere, notably integrating the fluxes of water, energy and geochemical compounds. Water is able to execute these tasks because of anumber of exceptional properties: (1) high and universal dissolving power, essential for distributing geochemical material and to transport nutrients and to remove waste substances from living organisms (2) high surface tension, causing high capillary forces; together with osmotic forces, this enables water and solute transport within organisms and maintaining ahigh cellular tension. (3) large heat capacity and heat of vaporisation, inherent to its role as energy transporter (4) maximum density above freezing point, at 4C; this anomaly causes freezing to proceed from thesurface downward, slowing down both theheat release and theadvancement of thefreezing process, thus protecting living organisms (5) high freezing and boiling point relative to its molecular weight, in comparison with similarly structured compounds, such as H2S and H2Se; compared to these compounds, these temperatures would be between 50 and 100C. All these properties are related to thehigh cohesion and pseudo-crystalline structure of water. This structure is caused by theeccentricity of thepositive hydrogen nuclei with respect
1)

to theelectrons and theoxygen nucleus, which gives theH2O molecule an electrical polarity or dipole character. In this chapter we will discuss thecomposition of thehydrosphere and thebasic concepts of thehydrological cycle and its interaction with atmospheric circulation. Subsequently, we will consider theindividual elements of thehydrological cycle, and their mutual interaction. Finally, attention is paid to theimpact of climatic change and mans interference with thehydrological cycle. 1.2. The Hydrosphere 1.2.1. Origin of water on Earth Most probably water has been in our solar system from thebeginning and was formed by thethermonuclear fusion process that produced theelements of theperiodic system and their compounds. Thetotal amount of water contained on Earth is estimated at some 0.4% by volume, sufficient to form asphere of ice with adiameter of almost 2500km and avolume of 8.2109km3. Most of this water is chemically and physically bound in rocks and minerals within thecrust and mantle. Theamount of free water, forming thehydrosphere, is estimated at 1.4109km3 i.e. 17% of thetotal amount of water on Earth of which 96% is stored in theoceans as saline water. It is generally accepted that most of thewater in thehydrosphere has originated from degassing of theEarths mantle by volcanic eruptions and surfacing lava (basalt) in thecourse of the5 billion years of theEarths existence. Theproduction by this process is estimated at about 1km3/year. However, it is known that Earth is also exposed to collisions with cosmic material, including ice comets. An extraterrestrial origin of at least part of theEarths water is therefore likely. Some of theother planets satellites and many comets consist almost completely of ice. Awell-known example is Halleys Comet. Arough estimate gives atotal amount of water in our solar system, that is 100000 times themass of water in our oceans[1].

Original version by J.J. de Vries, professor of hydrology, Free University, Amsterdam

INTRODUCTION

1.2.2.

The hydro-tectonic cycle

As explained before, theEarths hydrosphere acquires water both from themantle and possibly from space, again of theorder of 1km3/year. On theother hand, asmaller quantity escapes into space and another unknown amount returns to themantle through plate-tectonic processes. This process is driven by thermal convection currents, which move therigid lithosphere as acoherent layer over themore plastic asthenosphere (Fig.1.1). Magma moves upward into fractures (spreading centres) in the ocean floor, where it forms new oceanic crust. This causes thelithosphere to move away from thespreading centre. At theother limb of theconvection cell, thelithosphere sinks downward in asubduction zone. Where old lithosphere disappears in themantle, ocean water is dragged with thecrust to depths of hundreds of kilometres and becomes involved in there-melting of sediments into new magma. Another part of this water is exhaled again by

theassociated volcanic and magmatic activity. This entire process is referred to as thehydrotectonic cycle. This cycle acts on ageologic time scale of millions of years and is quantitatively negligible compared to theamount and distribution of water in thepresent hydrological circulation at theEarths surface and thelower atmosphere. Thedifference in dynamics of this hydrological cycle and thehydro-tectonic cycle is also reflected in therespective energy fluxes involved. Thedriving force behind thehydrological cycle, solar radiation, produces aflux at theEarths surface of 5.2109 J/m2/year, whereas thedriving force behind thetectonic processes, theEarths internal heat production, delivers about 2.0106 J/m2/year. Thevolcanic and magmatic exhalations, however, do have aqualitative effect on thehydrosphere by producing chemical compounds and concentrated heat. Volcanic dust and gases may influence theEarths heat balance and

Fig. 1.1. Schematic representation of thehydro-tectonic cycle, showing across-section through an ocean-continent boundary. Theupward moving mantle material forces theoceanic crust to slide under (to subduct) thecontinental crust. 1. Precipitation 2. Evapo(transpi)ration 3. Vapour transport 4. Topography driven flow (meteoric water) 5. Sea(water) trapped in subducted sediments (connate water) 6. Fluid released by deformation 7. Fluid released from magma and metamorphic reactions (juvenile water) 8. Volcanic emissions

The Global Cycle of water

thus its climate and hydrological cycle over aperiod of years. Plate-tectonics and continental drift change theshape of theearth on atime scale of millions of years by ageographic re-arrangement of oceans and continents, uplift of theEarths crust and theformation of mountain ranges. In thecourse of theEarths evolution these morphological changes have caused changes in worldwide climatic conditions and in thehydrosphere. Other long-term influences on theplanets climate are caused by systematic shifts in theEarths orbit and exposure to thesun, with associated changes in incoming solar radiation, on time scales of 104 to 105 years.

1.2.3.

Distribution of water over thevarious reservoirs

Thehydrosphere can be characterised as asystem of different reservoirs from which water, solutes and energy are exchanged by thehydrological cycle. On alarge scale this circulation is driven by thermal energy of solar radiation and by potential- and pressure energy produced by gravity. On asmall scale, capillary and osmotic forces play arole in water transport in soil and plants, whereas geothermal energy produces thermo-mineral convection currents in deep aquifers. As mentioned before, thetotal amount of water in thehydrosphere is estimated at 1.4109km3, of which 96% resides in theoceans. Theremaining 4% consists of freshwater, which exists and moves only by thevirtue of thecontinuous distil-

TABLE 1.1. Volumes and fluxes of water and their turn-over time in thedifferent compartments of thehydrosphere. Thevolumes are mainly according to [2], with some additions.
Volume in 103km3 Salt water Oceans Freshwater Ice Groundwater Lakes Soil moisture Atmosphere Reservoirs Rivers Biomass Total 27800 8000* 220** 70 15.5 5 2 2 40114 69.3 29.9 0.55 0.18 0.038 0.013 0.005 0.005 100 40 0.05 f 90 496 0.48 d 0.03 e 2.4 15 12000 b 500 c 1350 000 425 3000 a % of total freshwater flux 103km3/year turn-over time year

* < 5000m depth, based on aporosity of 1%, rather than porosity of 1.5%, resulting in avolume of 12106km3 (see VolumeV) ** about 50% contains salt or brackish water; cf. volume of 177103km3 (VolumeIII) a Flux is oceanic evaporation b Flux estimated from discharge c Flux estimated at 37% of total continental discharge (base flow) d Flux estimated at 80% of continental rainfall e Flux is total rainfall=total evaporation f Flux is total discharge from continents

INTRODUCTION

lation process that turns salt water into afreshwater by evaporation and subsequent condensation. Most of this freshwater is more or less locked up in ice caps, icebergs and glaciers, notably on Antarctica and Greenland. Were it to melt, theworlds rivers could flow uninterruptedly for more than 500 years on this quantity of water. An estimate of thedistribution of freshwater over thevarious global reservoirs and theturnover time of thedifferent reservoirs is given in Table1.1. There is considerable uncertainty about some of these figures, especially for groundwater at greater depths. Also estimates of theice volume vary considerably, from 22000km3 to 43000km3 . Most of thefreshwater reserve actively involved in thehydrological cycle is found in theupper few kilometres of thesubsurface. Thestate of thestill deeper water is not well known, but most of it is more or less isolated from thehydrological cycle by impervious layers and takes part in it only on ageological time scale. Moreover, most of this water is saline and probably mainly connate, i.e. water (mainly sea water) that was trapped during thedeposition of sediments. Part of this water is diagenetically altered meteoric water (i.e. from atmospheric origin) or juvenile magmatic water. Hot brines with atemperature of 200C are still encountered in theultra-deep Kola Peninsula (N.Russia) borehole at adepth of 12km. Such mineralised waters normally reach thesurface in thermo-mineral springs connected with (past-)volcanism or deepseated fractures (Fig.1.1). Another part of thegroundwater reserves (VolumeV, Chapter 1) at more shallow depths can also be classified as fossil, if this water was formed under different conditions than at present and if it is isolated from active circulation, either by less pervious layers or because of alack of recharge, like in arid regions. Ahuge groundwater reservoir (more than 100000km3 ) is present beneath theSahara and theArabian Peninsula in sandstones and limestones locally reaching athickness of 3000m. This water was dated at 1000040000 years BP and was recharged during pluvial periods in thelast ice age. It is still flowing under artesian pressure and constitutes thesource behind oases. Although this water is not actively involved in thehydrological cycle, its discharge adds water to theactive part, thus adding to theoceanic reservoir. Depletion of all fossil 4

reserves on Earth, either by natural discharge or by artificial extraction, would rise theaverage sea level by several decimetres. Another relatively slow part of thecycle is formed by thepolar ice caps which, at least on ageological time scale, must be considered atemporary phenomenon. They have been gradually formed since thetemperature at theEarths surface started to decrease at thebeginning of theTertiary, some 50million years ago, from about 20C to thepresent 15C. This eventually resulted 2million years ago in thepresent Quaternary with glacial cycles of theorder of 100000 years and temperature intervals of less than 10C. During more than 90% of theEarths history there were no polar ice caps. Theorigin of this cooling of theEarth is not fully understood, but ashift of theAntarctic landmass and theisolation of this continent by acircum-Antarctic ocean current during theTertiary and thesubsequent uplift of this continent was certainly aprerequisite for theinitiation of thehuge continental ice cap. Thegrowth of theAntarctic land-ice probably began during theMiddle Miocene, about 12million years ago, but the first glaciers on the Antarctic highlands originate from thebeginning of theOligocene, about 30million ago. 1.3. Theglobal water budget Aschematic overview of theglobal hydrological cycle and water balance is presented in Fig.1.2. Thehydrological cycle starts with evaporation from theoceans, estimated at 425000km3 (1176mm) per year. Rainfall over theoceans is estimated at 385000km3 (1066mm), leaving an excess of 40000km3 (equivalent to 110mm) of water as vapour, which is transported by atmospheric circulation (advection) to thecontinents. The main vapour flux travels from the warm equatorial to thecool high-latitude regions. Thevapour convergence at higher latitudes becomes clear from theareal distribution of theatmospheric vapour: theaverage annual vapour content decreases from 50mm water equivalent in equatorial regions to less than 5mm over thepolar regions. Condensation of the40000km3 of vapour originating from theoceans produces rain on thecontinents. This precipitation is repeatedly recycled by re-evaporation. Theannual cumulative evapotranspiration from thecontinents is estimated at 71000km3 (480 mm) so that finally atotal amount of 40000 + 71000=111000km3

The Global Cycle of water

Fig. 1.2. Schematic representation of theglobal hydrological cycle. Theoverall figures refer to thewater fluxes in 103km3 per year (according to Table1.2).

(746mm) of precipitation is produced, leaving an excess of 40000km3 (266mm) returning to theoceans via rivers, glacial meltwater and groundwater. Table1.2 shows thefluxes. 1.4. Components of thehydrological cycle 1.4.1. Evaporation Evaporation can only occur where avapour pressure gradient is maintained between theevaporat-

ing surface and theoverlying atmosphere. Besides this mechanism, evaporation also needs energy to convert water into vapour (2.44 103J/g at 15C). This energy is provided by theevaporating water, and indirectly from solar radiation and heat from theatmosphere. In fact, two factors control themechanism of evaporation. In thefirst place thedifference between thevapour pressure of theoverlying air (eA) and thesaturated vapour pressure (eS) at thetemperature of theevaporating surface. This difference (eSeA) is called thesaturation deficit. Secondly, the evaporation rate is

TABLE 1.2. Annual water balance at thevarious oceans and continents of theEarth [2].
Continents Surface area in 10 km
6 2

Oceans 361 (103km3) 385 425 40 458 505 47 (mm) 1066 1176 110 1270 1400 130

TheEarth 510 (103km3) 496 496 577 577 (mm) 973 973 1131 1131

149 (103km3) (mm) 746 480 266 800 487 313

After [2] Precipitation Evapo(transpi)ration Discharge After [3] Precipitation Evapo(transpi)ration Discharge 119 72 47 111 71 40

Note: [3] arrived at notably higher values for theoceans.

INTRODUCTION

determined by thevapour transport. Theupward movement in athin boundary layer is by molecular diffusion, but above this layer vapour is transferred and removed by turbulent air movement, related to thewind speed. Evaporation is strongly dependent on thetemperature determining thesaturated vapour pressure, and theturbulent air exchange that is related to wind speed and surface roughness. Methods to determine evaporation from climatic data are normally based on acombination of the energy balance for a specific surface and theaerodynamic conditions. Themost well known energy balance/aerodynamic method was developed by [4]. Later [5] adapted Penmans formula so as to make it applicable to vegetated surfaces as well, by introducing biological and aerodynamic resistance factors that incorporates structure and physiology of thevegetation cover. Although evaporation is driven by solar energy, the distribution over the oceans does not reflect thelatitudinal pattern of incoming radiation, neither in time nor place. This is because thelatent heat is for alarge part extracted from theheat stored in thewater itself, and thus influenced by warm and cold ocean currents. This occurs especially when relatively cold and dry air blows over awarm ocean current. Thehigh vapour pressure gradient between thewarm water surface and thedry air stimulates upward vapour transport and theenergy will be extracted mainly from thewater. Therefore, maximum evaporation occurs in theWestern Pacific and theWestern Atlantic where this particular situation prevails (Fig. 1.3). Relatively low values are found in theequatorial areas because of low wind velocity and high vapour pressure. Advection of warm air masses and seasonal variations in wind speed and turbulent exchange are other factors that influence thedistribution of evaporation over theoceans in space and time. Evaporation from avegetated land surface is normally acombination of direct evaporation from awet surface, and water consumption or transpiration by thevegetation. This combined effect is called evapotranspiration. Theevaporation from an extensive water surface, like alake or ocean, depends exclusively on theavailable energy and theatmospheric condition. Evaporation from aland surface however is often limited by theavailability of water. For awell-watered vegetated surface or awet soil, evaporation is nor6

mally close to that of an open water surface and is indicated as potential evapotranspiration. Theamount and thetiming of rainfall is an important factor. Available energy, for instance, can become thelimiting factor if rainfall occurs during thewinter season, whereas at theother hand, more regularly distributed rainfall with frequent showers can increase evaporation from interception. Limited amounts of water at theright moment and place is one reason that thetotal evaporation on thecontinents is less than half of theamount on theoceans. Theother factor is thelower net solar radiation received by theland surface. This is mainly caused by thedifference in albedo (percentage incoming solar radiation that is reflected back into theatmosphere at theEarths surface), which is 6 10% for open water and varies on thecontinents from 7% for tropical rain forest to 35% for dry white sand (see also Sect.1.4.3). 1.4.2. Precipitation and atmospheric circulation

In principle, rain is caused by condensation and cloud formation in theatmosphere when air is cooled to its dew-point. Thecooling is normally caused by adiabatic expansion of theuplifted air, due to thedecrease in atmospheric pressure with height. Heat release by condensation can subsequently provide additional energy to cause further rise of theair mass, which can result in convective thunderstorms. Most rain-producing vapour has been subjected to advective transport by atmospheric circulation. Thegeneral atmospheric circulation is maintained by thegradient in incoming solar radiation, with an excess in thetropical belt where receipt of heat exceeds thelosses back into space, and apermanent heat sink in thepolar regions. Heat consumption and heat release by evaporation and condensation, respectively, are asecondary factor in theglobal heat distribution. Theair movement itself is driven by thepressure gradient, which is caused by spatial differences in heating, but themovement deviates from thepressure gradient because of theEarths rotation (theCoriolis effect). Other deviations superimposed on thegeneral north-south circulation are due to thedistribution of land and sea and theassociated differential heating, including seasonal effects. Wind fields are further influenced by mountain ranges.

The Global Cycle of water

Fig. 1.3. Global pattern of annual evaporation in cm [6]; after [7].

At low latitudes theair column rises and moves poleward on either side of theequator. At higher latitudes cooling air causes thecolumn to descend. This results in thedevelopment of thelarge convective wind cells, theso-called Hadley Cells, with low pressure along theequator and high pressure around 30 Latitude. TheEarths rotation causes theseparation of thehigh pressure belt into divergent spiralling anticyclonic cells. Thecompensating back- flowing air produces the northeasterly and south-easterly trade winds, which converge in theequatorial area, and is therefore also known as theInter-Tropical Convergence Zone (ITCZ). Therising air along theequatorial convergence zone produces thehigh rainfall of thewet-tropical rainforest areas, whereas thehigh pressure belt with its heating of theair by compression, results in thelow rainfall zone of thedry-tropical steppe and desert areas. These arid zones extend northwards in theremote interiors of thenorthern hemisphere because of their distance from themoist oceanic air (Fig.1.4). Part of thewarm air from thesub-tropical high pressure belt moves to higher latitudes and forms theprevailing Westerlies on theNorthern Hemisphere. Cold air sinks at thepoles, spreads along an easterly course and clashes at mid-latitudes with theWesterlies. Here thewarm subtropical air overrides thepolar air and forms theso called polar fronts along thedifferent air masses.

Theforced uplift of warm moist air, together with low pressure pulsations in themeandering Jetstreams in theupper part of theWesterlies, causes thedevelopment of low pressure cells (anticyclonic cells). Their inward and convergent, spiralling movement forces themoist air to rise and produces thefrontal rains of themid-latitudes. Convective rains are formed mainly during thesummer in this area by free convection cells in overheated air. Extreme cases of convective rains are connected with thedevelopment of devastating hurricanes or typhoons. These develop in sub-tropical areas when low pressure convection cells form over warm sea surfaces of more than 260 C. Their energy is derived from theheat that is released by condensation of therising and expanding air. This process is self- sustaining because thewarm moist air is continuously sucked up from theocean. Extreme rainfall of theorder of 500mm/day is not uncommon during thepassage of hurricanes. Other heavy rain producing winds are theseasonal Monsoons. These represent wind systems that reverse their direction because of theseasonal change from high pressure to low pressure over large continental areas. TheIndian Monsoon is particularly strong. During thesummer theIndian subcontinent becomes very hot and astrong thermal low-pressure cell develops. Humid air 7

INTRODUCTION

Fig. 1.4. Theglobal pattern of annual precipitation [8].

from theocean moves in and brings high rainfall. Asimilar effect is caused by thesouthward shifting ITCZ during thesouthern hemisphere summer, bringing seasonal rain in thesub-tropics of southern Africa. Orographic effects are other causes of regional deviations in theglobal pattern. High rainfall generally occurs at the flank where air is forced upward and low rainfall is consequently observed at thelee side. 1.4.3. Discharge from thecontinents

sequently re-evaporated, mainly via transpiration by thevegetation. Groundwater at adepth of more than 1 to 2m below theroot zone hardly participates in theevaporation process, because capillary transport from thewater table upwards is then negligible. It is important to realise that two-third of continental rainfall originates from this re-evaporation and transpiration from land surfaces. Theexcess of surface water as well as groundwater is eventually discharged by rivers and to aless extent by direct groundwater discharge into thesea. Thecharacter of rivers, or theriver regime, follows mainly theseasonal pattern of rainfall and evapotranspiration with an attenuation and delay by thestorage processes. Rivers respond fast in areas with shallow soils on steep slopes and low infiltration capacity. In contrast, level areas with high infiltration capacity, high subsurface storage and high permeability, are characterised by slowly reacting rivers and the production of extended base flow. The total global discharge is released partly by base flow and partly by flood flow. Flood flow is not exclusively generated by surface runoff. Thelatter type of flow, in fact, occurs only during exceptional

Part of therainfall that reaches theearth will disappear again by evaporation, either directly from thewet soil surface or from interception on thevegetation. Theremaining water may partly run off along thesurface and partly infiltrate, recharging soil moisture (Volume V, Chapter 1). Soil water will percolate further downward to thesaturated zone (or groundwater zone) after thesoil has reached asoil-specific concentration of moisture. Theremaining part is held against gravity by capillary and other forces. Part of thesoil moisture and shallow groundwater is sub8

The Global Cycle of water

high rainfall and in steep land with an impervious subsurface. Flood water is normally produced by a range of processes, including rapid flow through themacro-pores of theupper soil layers (throughflow) and infiltration-excess or saturation-overland flow. These (near)surface processes normally initiate rills and gullies to participate in thedrainage process during periods of high or extended rainfall, so that thedrainage system expands into an ephemeral and poorly defined system of branches and associated depressions. Soil moisture plays an important role in theexchange of water and energy with theatmosphere. Wet soils absorb and store energy and contribute to thereturn of moisture to theatmosphere by evapotranspiration. Part of this vapour is eventually recycled as rain in thesame zone, or reappears as advective rain in adjoining areas. Water often disappears rapidly from dry and barren soil by sheet floods. Such surfaces receive less energy because of their higher reflection rate, increasing from 5 15% for dark, wet soils and vegetated surfaces, to 2545% for dry, light sand. In general, removal of vegetation similarly causes unfavourable conditions; notably in semi-arid regions this can inhibit thegeneration of convective rain. Under specific conditions of high infiltration capacity, a reduction of vegetation with its high water consumption can result in an increase in groundwater replenishment. However, an enhancement of groundwater recharge is not always desirable, as semi-arid areas in Australia exemplify. Removal of thevegetation in parts of this country resulted in arapid rise of thegroundwater table to near or at thesurface. Evaporation of this water causes severe and under thepresent climatic conditions irreversible salinisation (see Sect.1.4.4). Now we can consider therainfall-runoff balance on thecontinental scale (Fig.1.5). Average annual rainfall on thecontinents (estimated at 746mm) represents asurplus of 50% over average annual evapotranspiration (480mm), although on average theannual potential evaporation is higher than rainfall. This is because rainfall in many areas exceeds themaximum evaporation in one season, whereas maximum evaporation is not reached due to alack of water in other seasons. Changes in storage of soil water and groundwater play an important role in thesmoothing of these seasonal effects, and are therefore crucial for theconversion of precipitation into runoff.

Thereasons are (i) because of their buffering effect on thedischarge itself, and (ii) because they extend theevaporation beyond therainy period into thesubsequent drier period and thus increase total evapotranspiration. Thethree components of thehydrological cycle over thecontinents and oceans are listed in Table 1.2. There is aglobal seasonal effect in therunoff that is predominantly caused by thedetention storage of snow on thecontinents of thenorthern hemisphere. TheNorth American and Eurasian landmasses receive asnow cover over 60 70% of its surface, which reaches its maximum in March-April. Themaximum seasonal depletion of this cover follows at theend of thesummer, causing amaximum storage in theocean around October. Furthermore, the distribution of precipitation, evaporation and inflow from the continents eventually produces asurplus in theIndian and Atlantic Oceans, and anet loss from thePacific and theArctic Ocean. Consequently, there is a continuous inflow from the Indian and Atlantic oceans into the Pacific and theArctic oceans. Table1.3 shows thewater balance between precipitation, evaporation and discharge specifically over thevarious continents and oceans. 1.4.4. Groundwater

Thesubsurface consists of an upper zone with soil water and alower saturated part with groundwater; these zones are separated by thegroundwater table. Thedepth at which groundwater is encountered depends on topography, subsurface structure and climate. Total storage of groundwater in alayer is determined by theporosity, but the ease at which groundwater can flow depends on acombination of interconnection and size of thepores. This property is parameterised in thepermeability. High porosity and high permeability are notably found in alluvial sandy deposits and to alesser extent in sandstone. Clay on thecontrary shows about thesame porosity as sand (30 50 vol %), but thepores are small and consequently theflow resistance is considerable, so that saturated water flow is often negligible. Karstified limestone can produce very high permeability due to dissolution features, and can even develop subsurface streams. Relatively porous and permeable subsurface layers are indicated as water bearing layers and are called aquifers. Generally, claystones and crystalline rocks show 9

INTRODUCTION

poor aquifer characteristics, but weathering, fracturing and jointing can locally produce permeable structures. Groundwater recharge normally takes place by diffuse infiltration according to the processes described in Sect. 1.4.3. Concentrated recharge takes place via water that has accumulated in depressions or streams in cases where thestream bed is above thegroundwater table. Thelatter situation especially occurs in arid areas where deep groundwater tables prevail. Recharge is then from episodic floods in wadis or from river inflow from surrounding, more humid areas. Complete streams sometimes disappear underground in karstified limestones of high dissolution permeability. Groundwater discharge normally takes place by subsurface drainage to streams. Theaverage turnover time of groundwater is determined by thetotal flux, or recharge, and the storage of the basin. The flow density however, normally decreases downward, so that theage of thewater roughly increases logarithmically with depth (see VolumeIV). Water is stored during periods of high recharge: this results in arise of thegroundwater table and an increase of thehydraulic gradient, so

that thedischarge increases. Moreover, arise of thegroundwater table often means that lowerorder and less deeply incised stream branches are activated to take part in thedrainage process, which can amplify thedrainage rate by an order of magnitude. Saturation-excess overland flow through rills and gullies is theextreme condition which occurs when thegroundwater table reaches thesurface (Sect.1.4.3). Adry period reverses theprocess: groundwater is then released from storage because discharge exceeds recharge. Consequently thegroundwater table drops, discharge decreases and stops when thewater table at thedivide has reached thelevel of thedeepest incised channel and thehydraulic gradient has become zero. In arid areas where recharge is low and groundwater tables are deep, groundwater flow is more steady and fluctuations are dominated by long term cycles of drought and wet climatic spells. Residence times of groundwater range between months for shallow drainage systems to thousands of years for deeper systems, and especially in arid areas with low recharge and large turnover time. Exceptional cases of fossil or residual groundwater flow can be found in extensive groundwater basins in desert areas. Their relaxation time is large because of alarge volume of water stored

Fig. 1.5. Global pattern of annual runoff in cm [9]; after [10].

10

The Global Cycle of water

and because of a high flow resistance, due to thelarge distances between (palaeo-)recharge and discharge areas. An example is theSahara where huge fossil groundwater reserves from thelast ice age (dated 1000040000 years BP) still flow and feed springs, driven by aresidual hydraulic gradient. Thehydraulic gradient is slowly decreasing by depletion, but this process can proceed for thousands of years to come, unless largescale groundwater abstraction, like in theMiddle East, accelerates thedepletion. Thegroundwater systems discussed above are mainly driven by topography or potential energy, and their water is of meteoric origin. Groundwater occurrences at greater depths below impervious layers are more or less isolated from theactive part of thehydrological cycle and their character is partly connate; i.e. they were trapped during sedimentation and are often of marine origin. These waters therefore form theconnection with thegeological cycle of erosion, sedimentation, diagenesis, tectonics and metamorphism, and their dynamics are interlinked with these processes. Their flow is driven by processes on ageological time and areal scale, including compaction by sediment accumulation, pressure

change by tectonic deformation, thermal and geochemical convection, molecular diffusion and osmotic processes. Fluid movement under these conditions has often residual components because of thelong relaxation time of thepressure gradient. Theinteraction of these deep seated systems with theactive or meteoric part of thehydrological cycle occurs by slow upward seepage and in thermal and mineral springs in tectonically active areas. Groundwater and surface water in humid areas finally assemble in rivers which carry thecontinental surplus water back to theoceans. For this purpose, stream systems consist of ahighly efficient network of hierarchic and nested branches, each having their own sub-catchment. This network forms adynamic drainage and discharge system that expands into thesmallest gullies in time of high water supply, and contracts to thelarger ones in dry periods. Many arid basins do not produce awater surplus and maintain an internal ground- and surface water drainage. All rainwater eventually evaporates and thedissolved salts present in thewater are left behind. Thesalinisation of large areas in

TABLE 1.3. Annual water balance of continents and oceans [2]. P=precipitation, E= evaporation, D= discharge
Area (103km2) Europe Asia Africa Australia id. w.o. islands N. America S. America Antarctica All continents Arctic Ocean Atlantic Ocean Indian Ocean Pacific Ocean All oceans 10 44.1 29.8 8.9 7.6 24.1 17.9 14.1 148.9 8.5 98.0 77.7 176.9 361.1 P (103km3) (mm) 6.6 30.7 20.7 7.1 3.4 15.6 28.0 2.4 111 0.8 74.6 81 228.5 385 657 696 696 803 447 645 1564 170 746 97 761 1043 1292 1066 E (103km3) (mm) 3.8 18.5 17.3 4.7 3.2 9.7 16.9 0.4 71.3 0.4 111.1 11.5 212.6 224.7 375 420 582 534 420 403 946 28 480 53 1133 1294 1202 1176 D (103km3) (mm) 2.8 12.2 3.4 2.4 0.2 5.9 11.1 2.0 39.7 0.4 36.5 19.5 15.9 39.7 282 276 114 296 27 242 618 142 266 44 372 251 90 110 D/P (%) 43 40 16 33 6 38 40 83 36 45 49 24 7 10

11

INTRODUCTION

Australia, for instance, is due to evaporation of rising groundwater, which is loaded with theaccumulated salt. Most of these areas experienced wet pluvial conditions during thelast ice age but started with theaccumulation of salt some 10000 years ago at thebeginning of thedrier Holocene. 1.4.5. Continental water surplus and water use

tions of theregional water balance have certainly resulted in a modification of the regional atmospheric and hydrological circulation and theassociated climate (Sect.1.5.2). Water resources assessment and sustainable resource development and management require asound knowledge of thehydrological processes involved. Especially VolumeV of this series is devoted to these aspects. Numerous tools and models which have been developed for analysing thehydrological situation are being treated in VolumeVI. 1.5. Thehydrosphere and global change 1.5.1. Climatic change TheEarth forms adynamic system, with internal processes driven by internal heat production and external processes driven by solar energy. Both type of processes interact in cycles of material and energy flows, each with its own temporal and spatial scales. Ashift in one of thecomponents must lead to an adjustment elsewhere in thesystem, which in turn can trigger changes in related systems. Regional hydrological cycles are closely linked with theprevailing climatic conditions and associated vegetation covers, and can be expected to react accordingly to changes in themeteorological forcing or large-scale transformation in surface cover. As explained before, thepresent climate deviates from theaverage climate during theEarths history and is characterised by relatively low temperatures and ice caps at thepoles. Thepresent ice age is thesixth over thelast billion years, and was preceded by thePermian glaciation some 250million years ago. Apart from these cold eras, theEarth has experienced shifts from thedomination of wet and hot swamps, as during theCarboniferous, to thehot and dry prevailing desert conditions during theTriassic. Such major shifts are basically caused by plate-tectonics induced shifts in thegeographical position of thecontinents as well as by changes in their elevation by uplift and mountain building. Another major player in theglobal climatic system is probably thecarbon-dioxide content of theatmosphere. CO2 is part of theglobal geochemical carbon cycle which has thefollowing main fluxes: (i) CO2 extracted from theatmo-

Aspecial component of thecontinental water balance is theuse and diversion of part of thewater surplus by man. Theestimated annual 40000 km3 (266mm) of runoff from thecontinents (Table1.2) represents theexcess water that is left of the111000km3 (746mm) of rainfall, after evaporation and transpiration by natural vegetation and rain-fed agriculture have taken their share. In principle, this excess water is available for domestic and industrial use and for irrigated agriculture. About 5000km3 of this water is nowadays withdrawn for these purposes. Irrigated agriculture takes thehighest share with 65%. It is responsible for more than 50% of theworlds food production on 20% of theworlds arable land. Thehigh amount of water needed for food production is exemplified by thefact that theproduction of 103 kg of corn, sufficient to feed six people for one year, requires 300103 kg of water under average climatic conditions. Theratio between water use and dry mass accretion differs between crops and depends obviously on climatic conditions, particularly thepotential evaporation. Observations on various types of vegetation give values between 100 and 1000 kg of water per kg dry mass production. Theuneven distribution of water resources in time and space and theirregular spread of theworlds population, restrict thepossibilities for increasing theapplication of this excess water. Most of thewater is available in theequatorial tropical areas (theAmazon River, for instance, discharges 20% of theworlds total runoff), whereas twothirds of mankind live outside thetropics. Another negative factor is thevariability of thesupply in time. Only one-third of therunoff forms amore or less stable supply, while theremaining part occurs in floods. Theirregular distribution of water in space and time has led from theearliest civilisations onwards to hydraulic engineering practices, notably theconstruction of water diversion, transport and storage works, including large-scale drainage and irrigation schemes. These modifica12

The Global Cycle of water

sphere by photosynthesis, producing organic material, and by weathering of rock as well as deposition of calcium minerals; (ii) CO2 released to theatmosphere by decay of organic matter and respiration by plants and soils; (iii) CO2 periodically evading from and taken up by theoceans; (iv) CO2 recycling in theEarths interior by absorption in themantle via thedescending subduction zone and release through degassing by volcanic eruptions and by theextrusion of magma in theoceanic ridges (Fig.1.1). Theoceans form alarge CO2 reservoir that act as abuffer through their physico-chemical diffusion exchange with theatmosphere. Algae play an important role in this process. An illustration of thepossible influence of thegeographical position of continents and oceans, and theopening up and closing of ocean basins, as well as theinfluence of atmospheric levels of CO2, is presented by thechange in conditions when going from theCretaceous to theQuaternary era. Theelevation of thecontinents was much lower than at present, and theocean-land ratio much larger, especially during thesecond half of theCretaceous. TheAntarctic Ocean was not yet isolated from warm ocean currents, whereas thelandmass at theArctic was isolated and situated far from snow producing oceans. Moreover, geochemical budget modelling suggests that theCO2 content of theatmosphere during thelast 500million years was several times higher than at present, with amaximum of 18 times thepresent content in themid-Cretaceous, some 100million years ago. During themid-Cretaceous thetemperature of deep ocean water was 150 higher than at present and corals were found 1500km nearer to thepoles. At theonset of theTertiary, about 60million years ago, thetemperature gradually decreased, probably because of athermal isolation of thepolar regions. Theseparation of Antarctica from theAustralian continent and theshift of this landmass to theSouth Pole led to thedevelopment of acircum-Antarctic ocean current that obstructs theheath exchange with warm ocean water and allowed theaccumulation of snow. TheArctic opened up and came under theinfluence of precipitation-producing ocean water, but at thesame time remained to acertain extent blocked by surrounding continents. Concurrently, theAntarctic landmass rose, which contributed further to thecooling. Probably already during theOligocene mountain glaciers were formed on

thehighest mountains. Ice caps began to develop by themid-Miocene, about 10million years ago. This had apositive feedback effect, firstly by an increase in thealbedo, resulting in areduction of thenet radiation, and secondly by afurther rise of land surface by ice accumulation by more than 1000m. Thelatter effect is still clear in theArctic where Greenland with an altitude of over 2000m is still glaciated, whereas theCanadian Arctic at thesame latitude only shows awinter snow cover. Theelevation effect on temperature is adecrease of 6C/km under present conditions. Another effect may have been thecontinental uplift of other Alpine mountains in thecourse of theTertiary, notably theelevated areas of theHimalayas and theTibetan Plateau with their associated cooling and blocking effect on atmospheric circulation. This orogenesis also caused an increase in weathering and erosion with its associated consumption of atmospheric CO2. TheQuaternary glacial period, which began about 2.5million years ago with apronounced fall in temperature, is characterised by 15 to 20glacial-interglacial cycles. During themaximum glaciations, air temperatures at thetemperate climate zone dropped by 60 C relative to present temperature. It is generally accepted now that these cyclic fluctuations were primarily triggered by minor variations in theamounts of solar radiation reaching thetop of theatmosphere. These variations originate from regular oscillations in (i) theEarths orbit (periodicity about 100 000 years), (ii) thetilt of theEarths axis (41 000 years), and (iii) acircular movement (wobble) of thespin of theEarths axis (23 000 years). These are called theMilankovitch oscillations after theSerbian engineer and astronomer Milutin Milankovitch who investigated these astronomical factors and their possible climatic impact at thebeginning of the20th century. Superimposed on the20 000 100 000 years astronomically driven climatic oscillations are relatively strong fluctuations in temperature on atime scale of hundreds of years during theglaciations. Fluctuations on similar time scale but lower amplitude have also been observed during thelast 10000 years, i.e. during thepresent (Holocene) climate. Within this climatic noise main shifts over periods of hundreds to thousands of years have been recognised in therecords of theHolocene. For themid latitudes of thenorthern hemisphere these climatic fluctuations seem 13

INTRODUCTION

to be connected with thepersistence of (i) periods of strong zonal flow of theWesterlies with strong oceanic influence, and (ii) periods with more polar and continental influence and a more southerly track of theWesterlies. This alternating system is dominated by thepattern of high and low pressure cells, which is probably influenced by shifts in ocean currents. Theimpact of theshift in pressure distribution seems to reach as far south as theSahel zone. Themost comprehensive review of climatic fluctuations in Western Europe and the Middle East was produced by [11]. His system is based on climatic proxy data (such as pollen, isotopes and tree-ring analysis), global circulation reconstructions and archaeological and historical information. Aschematic review of fluctuations in Holocene climate, mainly based on [11, 12], is thefollowing. 140008000 BC: end of glaciation; sudden and strong temperature fluctuations due to instability of glaciers and theproduction of huge masses of meltwater 80006000 BC: rapid warming and melting of mountain glaciers; humid environment in theMiddle East and savannah conditions in theSahara 50003500 BC: Post-Glacial Climatic Optimum: summer temperatures in NW Europe 23C above that of thepresent day; monsoonal rains penetrate theSahara; extensive irrigated agriculture in Mesopotamia 35001000 BC: drying of theSahara (35001000); desertification and salinisation in Mesopotamia, Nile flow reduced; sharp decline in temperature about 1500 BC with astrong advance and initiation of new mountain glaciers (it has been suggested that thelatter cooling might be connected with thehuge eruption of theSantorin volcano in theAegean Sea about 1450 BC) 900300 BC: Iron Age Epoch: Cool and wet in northern areas; strong regrowth of bogs after amuch drier period 400800 AD: severe North Sea floods; growth of Alpine glaciers 8001200 AD: Secondary (Early Medieval) Climatic Optimum: summer temperature at least 1C above present day; drier in NW Europe; Viking colonisation of Greenland 14

14301850 AD: Little Ice Age (polar continental climate): cool in W. Europe and theMediterranean; temperatures 1 3C lower than at present; re-advancement of mountain glaciers; severe winters 1850 AD present: maritime Atlantic climate; global temperature rise 0.5C; N. Atlantic sea surface warmer; increased rainfall in NW Europe. Our knowledge of the causes of these fluctuations is still imperfect and they are probably not thesame for thedifferent periods. Theexceeding of threshold values within theinternal instability of theatmosphere-ocean system, which triggers achain of feedback loops, is adistinct possibility. Other hypotheses focus on external factors, including variations in solar radiation (notably sun spot activity) and volcanic activity. Theincrease in temperature during thelast century may be attributed to theincrease in CO2 as caused by thecombustion of fossil fuel, and possibly to periodicities in thesolar activity as revealed by thesunspot numbers. Thelatter is in accordance with thelow sunspot activity during theLittle Ice Age, but themechanism behind this correlation is unclear and still amatter of debate. 1.5.2. Thehuman factor

Our knowledge of mans influence on theglobal hydrological cycle is minor and mainly restricted to thedirect consequences of water management for thewater balance and runoff regime on thesmall and medium catchment scale. Thelong term impact of large-scale manipulations of river basins and land use change is difficult to evaluate in theabsence of long-term hydrological data. Information on the influence of land use change on evapotranspiration is rather well known, but thelack of adequate models that couple theexchange of water and energy at thesurface with atmospheric circulation models make it difficult to translate this information into changes in rainfall pattern. It is even more problematic to reconstruct theeffects of thelarge-scale reclamation and cultivation practices during thelast 10000 years, i.e. since agriculture was introduced. Themost evident influence of mankind on thehydrological cycle from thedawn of civilisations is theapplication of irrigation and drainage. In fact, it seems that thetransition from gathering wild grains to thegrowth of cereal crops evolved

The Global Cycle of water

concurrently with thebeginning of diversion and control of flowing water. Theoldest traces of irrigated agriculture were found with theremains of theearly urban civilisation of Jericho, where already before 7000 BC water from alarge spring was applied for irrigation. Different views have been developed on theimpact of these early practices on theenvironment and on thequestion whether changes in climate or destructive land use and/or war caused desertification and salinisation and thefall of civilisations. Recent palaeoclimatic and archaeological research have made it plausible that wet and dry climatic episodes have often been thetrigger of disasters, but that man helped to aggravate thesituation. Less direct, but probably of more regional and even global influence, must have been the effects of thelarge-scale removal of thetemperate forests, and more recently thedestruction of tropical forests. This process began more than 2000 years ago in theMediterranean and China, 1000 years ago in Europe and 100 years ago in North America, and proceeds with thecurrent destruction of theequatorial rain forest by logging and slash-and-burn agriculture. In addition, large-scale drainage and reclamation works have destroyed wetlands. All these changes, together with urbanisation, must be held, at least in part, responsible for lower evaporation, accelerated discharge and increased flooding. Themain question is if, and how, these changes in soil moisture, evapotranspiration and catchment runoff regimes have caused anomalies within theregional dynamic equilibrium of thegeneral circulation, and how these in turn have affected rainfall. What we do know is that combustion of fossil fuel, irrigation and theloss of forest have caused an increase in theglobal atmospheric concentrations of greenhouse gasses CO2 and CH4. Theincrease rate in methane is twice that of carbon dioxide, while methane is 20 times as effective in its greenhouse effect as CO2. During thelast century, theCO2 concentration rose from 290 ppm to 350 ppm, whereas theCH4 concentration from 0.95 to 1.65 ppm. Theglobal rise in temperature of 0.3C during thelast century may well be connected with these increased emissions. At thesame time, arise in temperature will probably also result in ahigher cloud cover. This might counterbalance thegreenhouse effect by an increase in theatmospheric albedo. Thesame could apply for the influence of dust particles from

land clearance and industrial activities. However, thephysics of clouds and aerosols and their interaction with radiation is not sufficiently understood yet to assess these effects quantitatively. In the absence of concrete data, we will briefly and qualitatively summarise thepossible effects of therespective man-induced environmental changes on climatic-hydrological conditions (see VolumeV for amore detailed discussion). 1.5.2.1. Irrigation About 3500km3 of thesurplus water is now used for irrigation. Most of this water evaporates and theatmospheric moisture content will increase. Wet soils lower thealbedo and thus enhance net radiation. These effects together might stimulate convective rain, especially in semi-arid areas. Higher atmospheric moisture levels at theother hand might hamper themoisture influx from surrounding regions. 1.5.2.2. Wetland drainage Large-scale drainage of wetlands diminishes evapotranspiration. Thesame applies to largescale deforestation, because trees normally use more water than grassland or agricultural crops, partly because of high interception evaporation. This means that thetotal runoff from these areas must have increased, whereas streamflow regimes may have developed amore seasonal character due to theloss of retention storage. Losses of atmospheric moisture associated with reduced evaporation, and higher reflection may also have resulted in lower rainfall. [13], citing Russian sources, suggests that 10% of theprecipitation in temperate humid climates probably originates from local evaporation. Much higher values were recently suggested for theGreat Plains in theUSA. 1.1.1.1 Ground cover damage

Semi-arid areas are very susceptible to damage of ground cover. Thesoil will dry out and erode, rainfall will generate surface runoff instead of infiltration, evaporation will be reduced, thereflection from both thesurface and atmospheric dust particles may increase and convective rainfall might therefore decrease. Thechange in thermal and moisture regimes is then expected to result in an anomalous atmospheric situation that will 15

INTRODUCTION

be propagated by advection to surrounding areas. This may finally influence theatmospheric circulation on alarger scale. This may lead to desiccation and desertification over extensive areas. Theabove mentioned processes could be initiated if plans to drain thehuge swamps of theWhite Nile in theSudan materialise. Thesurface area of these Sudd swamps is about 34000km2 and can produce 25km3 water, which would double theWhite Niles discharge. Theconsequences for theregional rainfall are not yet known, but preliminary circulation modelling exercises suggest that 19% of thepresent January evaporation returns as rain on theSudd [13]. 1.5.2.3. Deforestation Deforestation of tropical forest also results in tremendous reduction of evapotranspiration and, ultimately, of rainfall. Whereas early simulations of large-scale conversion of, for instance, theAmazonian rain forest to pasture predicted major reductions in regional rainfall (up to 30%), more recent simulations based on improved models suggest amore limited effect. Particularly disastrous conditions are known to result from theclearing of tropical steep land forest. Sheet wash and flooding during thewet season are often followed by lack of water during thedry season, because of aloss of storage capacity in thesoil due to accelerated erosion [14]. 1.5.2.4. Interbasin diversion Theproposed large-scale interbasinal diversion schemes of theRussian Federation and theUSA would come to large-scale interferences in water circulation. Both envisage thetransfer of water from theArctic basins to thesouthern semi-arid areas. Both plans are shelved for thetime being for various, mainly political, reasons. One of thescientific objections against theRussian plans is thefear that asubstantial reduction of theinflow of freshwater in theArctic Ocean could result in asmaller ice cover during winter, accordingly reducing thealbedo. This would have amajor impact on theworlds heat balance. In China huge water management projects are planned and partly under construction, aiming at thetransfer of water from theYangtze River (and perhaps theBrahmaputra) to theHwang Ho basin in thedry northern plains around Beijing. 16

1.5.2.5. Streamflow management Most of thehuman endeavours to fight theirregularity in water supply are based on themanagement of stream flow. An alternative is the control of theatmosphere by triggering rain through cloud seeding. Many experiments have been carried out, but their effectivity is difficult to prove and thescientific results are subject to much controversy, not to speak of thesocial and legal aspects. Better forecast of local convective storms with radar and satellites might increase thesuccess of this technique in thefuture. 1.5.2.6. Land use changes Evidently, theimpact of large-scale water management schemes and changes in land use must create anomalies and changes in theregional moisture and heat budgets, which -by thegeneral circulation- may be propagated to distant regions. Evidence of this type of tele-connection is notably available from theocean-continent interaction. Aclear example is theinfluence of thesurface temperature anomaly in the tropical Pacific and theoccurrence of theEl Nino-circulation. Understanding of these processes with their regional and seasonal variability and feedback loops, and prediction of their effects, require an improvement in resolution of theGeneral Circulation Models (GCM). Earth observation by satellite remote sensing can be agreat help to monitor theinput variables, whereas theapplication of isotopic tracers is auseful tool in analysing flow paths of vapour and identifying recycling of moisture. Notably thequestion of moisture recycling is challenging, because until now climate models suggest alimited contribution of local evaporation to rainfall (see e.g. Sect. 1.5.2.4), whereas two-third of theprecipitation on acontinental scale originates from re-evaporated rainwater (Sect.1.4.3). 1.6. Isotopes in the hydrological cycle Theoriginal studies on isotopes in water were concerned with seawater and precipitation. Thefirst was primarily asurvey on variations in 18 O/16O concentration ratios, soon to be followed by astudy of the2H/1H ratios in natural waters [15]. [16] observed in great detail 18O/16O variations in global precipitation, including adiscussion on themeteorological patterns. His work was

The Global Cycle of water

thestart of theglobal isotopes-in-precipitation network of theinternational organisations WMO and IAEA. In more recent years theobservations became supported by theoretical and numerical modelling. The first study on 14C in groundwater, soon in combination with 13C/12C, was started by theHeidelberg group in thelate 1950s [17, 18]. In later years this methodology became an important tool in studying groundwater movement. Therevolutionary development of theintroduction of nuclear accelerators as mass spectrometers has greatly stimulated thehydrological application of isotopes with extreme low abundances in nature. Also 14C research has gained tremendously by this new technological approach. The first sections in this chapter have presented abroad picture of theglobal water cycle, consisting of theorigins of water, thesizes of theglobal water reservoirs and the fluxes between them. However, in our day-to-day life, where we are dealing with stream-flow management, drinking-water supply, thepropagation of theeffects of surface pollution underground, et cetera, we are no less confronted with regional water bodies, streams, lakes, aquifers, their sizes and their fluxes. It will be shown that the application of isotopes as they occur in nature are an invaluable help in studying thebehaviour of water and finding solutions for water problems. Theremainder of this volume and theother volumes of theseries are devoted to this. Thenature of theisotopic applications is of course dictated by the specific character of isotopes, radioactive and non-radioactive. We can distinguish three different types of applications. (1) Stable and radioactive isotopes can be used as tracers, marking awater body or acertain quantity of water; anice example is thephenomenon that therain water during aheavy storm is often depleted in theheavy isotope (stable 2H, deuterium, or stable 18O) with respect to themost abundant isotope (1H and 16 O, respectively). This offers thepossibility to follow therain water in thesurface runoff and even quantitatively analysing therunoff hydrograph. (2) During thetransition of compounds such as water or carbon dioxide from one phase to another, theconcentration ratio of theisotopes of an element often changes, undergoes

so-called isotope fractionation. Conversely, observing differences in especially thestable isotopic concentration ratios informs us about certain geochemical or hydrological processes that took place. For instance, as aresult of aseries of processes, theisotopic composition of carbon as well as oxygen of calcium carbonate is different for themarine and thefreshwater origin. Furthermore, theisotopic composition of oxygen and hydrogen in rainwater varies with latitude, altitude, climate and time of theyear. (3) Radioactive decay offers thepossibility to determine an age, provided certain conditions are met. Noteworthy in this respect is thefrequent application of dating groundwater i.e. determining thetime elapsed since the infiltration of the water- by comparing the14C or 3H (tritium) activities in agroundwater sample with that of therecharge water. Moreover, also concentration differences of radioactive isotopes can also be used as atracer. Thefollowing chapters serve to present and explain thefundamental background of theabundance and behaviour of isotopes in nature, as well as some practical information on sample handling and analysis. Thementioning of examples will be brief; theother volumes of this series are dealing with thevarious compartments of thewater cycle, treating therole of isotopic applications in detail. Besides theoccurrence of natural isotopes in our environment, man is able to produce radioactive isotopes. Also these can be applied as tracers, to follow water movement or reservoir leakage. Themethods of applying artificial tracers are parallel to theuse of chemical tracers, often recognisable by their fluorescent character. This methodology will not be themain subject of these volumes, despite themany successful applications. We will restrict ourselves to theisotopes found in our environment by nature. Only at few occasions we can not avoid mentioning theartificial isotopes. 17

ATOMIC SYSTEMATICS AND NUCLEAR STRUCTURe

2. ATOMIC SYSTEMATICS AND NUCLEAR STRUCTURe

In this chapter theprinciples and systematics of atomic and nuclear physics are summarised briefly, in order to introduce theexistence and characteristics of isotopes. 2.1. Atomic structure and theperiodic table of theelements Atoms consist of anucleus surrounded by electrons. Compared to thediameter of an atom, which is of theorder of 108cm, thesize of thenucleus is extremely small (~1012cm). Thedense concentration of matter of thenucleus mainly consists of two kinds of particles, neutrons and protons, which have about thesame mass. Theneutron carries no electric charge, while theproton is positively charged. Thenumber of protons (Z), theatomic number, is equal to thenumber of electrons surrounding thenucleus. Electrons have amass that is about 1/1800 that of theproton mass and carry an equal but negative electrical charge, so that theatom as awhole is neutral. Atoms missing one or more electrons are referred to as positive ions, atoms with anumber of electrons exceeding theatomic number are called negative ions. Protons and neutrons, thebuilding stones of thenucleus, are called nucleons. Thesum of thenumber of protons and neutrons (N) in anucleus is thenuclear mass number: A=Z + N (2.1) Thenotation describing aspecific nucleus (=nuclide) of element X is:
A Z XN

Because thechemical properties of an element (X) are primarily determined by thenumber of electrons in theatom, theatomic number Z characterises theelement. Therefore, writing AX alone defines thenuclide. Thecloud of electrons circulating around thenucleus is well structured and consists of shells, each containing amaximum number of electrons. Thechemical properties of an atom are now mainly determined by thenumber of electrons in theouter, incompletely filled electron shell. Because of this systematic, all atoms can be arranged in aPeriodic Table of theElements (part shown by Fig.2.1). 2.2. Structure of theatomic nucleus Theatomic nuclei are kept together by extremely strong forces between thenucleons (protons and neutrons) with avery small range. As repulsive electrical (Coulomb) forces exist between theprotons, thepresence of neutrons is required to stabilise thenucleus. In themost abundant nuclides of thelight elements, thenumbers of protons and neutrons are equal. Nuclei such as
2 1 1

He2
4 2

12 6

C6

14 7

N7

16 8

O8

are stable, as is thesingle proton (1H=hydrogen). For theheavy elements thenumber of neutrons far exceeds thenumber of protons: 238U contains only 92 protons, whereas thelargest stable nuclide, thelead isotope 208Pb has an atomic number of 82. Instabilities are caused by an excess of protons or neutrons. Examples of such unstable or radioactive nuclei are
3 1 2

H 14 C 6 8

For thelight elements, aslight excess of neutrons does not necessarily result in unstable nuclei:
Fig. 2.1. Part of the periodic table of the elements, containing thelight elements. Also shown are theelectronic configurations of therespective atoms.
13 6 17 18 C715 N 7 8 O 8 9 O 8 10

are stable. For these asymmetric nuclei (ZN) however, theprobability of formation during 19

INTRODUCTION

16

O N

17

18

14

15

12

C B

13

14

10

11

number of protons Z
6

Be

10

Be

Li

theperiodic table of theelements. An example of theoccurrence of themagic numbers is thelarge number of stable isotopes of lead: thelargest stable nuclide, 208Pb (with Z=82 and N=126) is double magic. Especially theuneven-uneven nuclei are unstable and have asmall chance of natural occurrence. Most uneven-Z elements have only one or at most two stable isotopes. Theearlier statement that thechemical properties of an element only depend on theatomic number, implying that thechemical properties of isotopes are equal, needs revision if we look in detail. Thefact is that in nature variable relative concentrations of isotopes are observed. There are two causes for this phenomenon: (1) thechemical and some physical properties of theisotopes of one element are not exactly equal, resulting in slightly different chemical and physical properties -and consequently different concentrations- of isotopic molecules, i.e. molecules that contain different isotopes of that element; (2) if theisotopes concerned are radioactive, theprocess of radioactive decay causes theconcentration of theisotopic molecules concerned to diminish in time; this may result in concentration differences that are much larger than as caused by theisotope processes as mentioned under 1). These phenomena will be discussed separately in thenext chapters. 2.4. Mass and energy It is inconvenient to use thereal mass of atoms and molecules. Instead we define the atomic mass as themass expressed in atomic mass units (amu). Originally this was equivalent to themass of aproton; later for practical reasons, theatomic mass unit has rather become defined as 1/12 times themass of a12C atom: 1 amu=1.66056551027 kg (2.2)

Li

He

He H number of neutrons N

H n

Fig. 2.2. Part of the chart of nuclides, containing thelight elements. The isotopes of an element (equal Z) are found in a horizontal row, isobars (equal A ) along diagonal lines, isotones (equal N) in vertical columns. The natural radioactive isotopes of H, Be, and C are marked grey.

thecreation of theelements, -nucleosynthesis-, was smaller, resulting in smaller natural concentrations for these nuclides. Thenaturally occurring stable and radioactive isotopes of thelight elements are shown in apart of theChart of Nuclides (Fig.2.2). Another part, showing some heavy nuclides is given by Fig.11.2. Note that in thehigher Arange N and Z are no longer about equal (238U with Z = 92 and N=146). 2.3. Stable and radioactive isotopes Theatomic nuclei of an element containing different numbers of neutrons are called isotopes (iso topos=at thesame place in theperiodic table of theelements). Many elements have two or more stable, naturally occurring isotopes. In general, nuclei with even numbers of protons or/ and neutrons are more stable. Nuclei of which thenumber of protons or/and neutrons corresponds to some specific even number, belonging to theseries of so-called magic numbers 2, 8, 20, 28, 50, 82, and 126, have arelatively high stability and consequently large natural occurrence. These magic numbers can be explained by anuclear shell model with closed nucleon shells within thenucleus, similar to theclosed electron shells in atoms, thebasis of theperiodicity in 20

In chemistry it is now convenient to use themole quantity, defined as thenumber of grams of theelement equal to theatomic weight. Thenumber of atoms in one mole of theelement or thenumber of molecules in one mole of achemical compound is then equal for any substance and given by Avogadros number=6.022521023.

ATOMIC SYSTEMATICS AND NUCLEAR STRUCTURe

If we now add up theatomic masses of thebuilding stones of acertain nucleus X, for instance of 12 C consisting of 6 protons and 6 neutrons, it appears that theatomic mass of X is smaller than thesum of the12 constituent particles: 6 protons= 61.007825 amu = 6.04695 amu 6 neutrons = 61.008665 amu = 6.05199 amu total mas = 12.09894 amu 12 compared to Aof C =12.00000amu (by definition) difference = 0.09894 amu This so-called mass defect has been converted into the binding energy, thepotential energy stored in thenucleus to keep theparticles together. This equivalence of mass and energy is defined by Einsteins special theory of relativity as

EB=Mc2

(2.3)

where EB is thebinding energy, M is themass, and c is thevelocity of light (2.997925108m/s). According to this definition the equivalence between mass and energy is expressed as 1 amu=931.5 MeV (million electronvolt) (2.4) where 1 eV=1.6021891019 J (electrical charge unit=electron charge= 1.6021891019C). All energies in nuclear physics, such as theparticle energies after nuclear decay, are presented in MeV or keV (kilo or 103 electronvolt). In our case of 12C thebinding energy turns out to be 0.09894 amu=931.5 MeV/amu=92.16 MeV or 7.68 MeV per nucleon.

21

abundance and fractionation of stable isotopes

3. Abundance and fractionation of stable isotopes

In classical chemistry isotopes of an element are regarded as having equal chemical properties. In reality variations in isotopic abundances occur far exceeding measuring precision. This phenomenon is thesubject of this section. 3.1. Isotope ratios and concentrations Before we can give amore quantitative description of isotope effects, we must define isotope abundances more carefully. Isotope (abundance) ratios are defined by theexpression R = abundance of rare isotope abundance of abundant isotope 3.2. Isotope fractionation According to classical chemistry, thechemical characteristics of isotopes, or rather of molecules that contain different isotopes of thesame element (such as 13CO2 and 12CO2) are equal. To alarge extent this is true. However, if ameasurement is sufficiently accurate and this is thecase with themodern mass spectrometers (Chapter 11) we observe tiny differences in chemical as well as physical behaviour of so-called isotopic molecules or isotopic compounds. Thephenomenon that these isotopic differences exist is called isotope fractionation. (Some authors refer to this phenomenon as isotope discrimination; however, we see no reason to deviate from theoriginal expression). This can occur as achange in isotopic composition by thetransition of acompound from one state to another (liquid water to water vapour) or into another compound (carbon dioxide into plant organic carbon), or it can manifest itself as adifference in isotopic composition between two compounds in chemical equilibrium (dissolved bicarbonate and carbon dioxide) or in physical equilibrium (liquid water and water vapour). Throughout this volume examples of all these phenomena will be discussed. Thedifferences in physical and chemical properties of isotopic compounds (i.e. chemical compounds consisting of molecules containing different isotopes of thesame element) are brought about by mass differences of theatomic nuclei. Theconsequences of these mass differences are two-fold: (1) Theheavier isotopic molecules have alower mobility. Thekinetic energy of amolecule is solely determined by temperature: kT=mv2 (k=Boltzmann constant, T=absolute temperature, m =molecular mass, v=average molecular velocity). Therefore, molecules have thesame mv2, regardless of their isotope content. This means that themolecules with larger m necessarily have asmaller v. Some practical consequences are: (a) heavier molecules have alower diffusion velocity; 23

(3.1) Theratio carries asuperscript before theratio symbol R, which refers to theisotope under consideration. For instance:
13

R(CO2) =

[13CO2] [12CO2] [2H1HO] [1H2O]

18

R(CO2) =

[C18O16O] [C16O2] [H218O] [H216O] (3.2)

R(H2O) =

18

R(H2O) =

We should clearly distinguish between an isotope ratio and an isotope concentration. For CO2 for instance, thelatter is defined by:
13 [13CO2] [13CO2] R = = 13 12 [CO2] 1+13R [ CO2]+[ CO2]

(3.3a)

Especially if therare isotope concentration is very large, as in thecase of labeled compounds, therare isotope concentration is often given in atom %. This is then related to theisotope ratio by: R=(atom %/100) / [1 - (atom %/100)] (3.3b)

INTRODUCTION

(b) thecollision frequency with other molecules theprimary condition for chemical reaction is smaller for heavier molecules; this is one of thereasons why, as arule, lighter molecules react faster. (2) Theheavier molecules generally have higher binding energies. Thechemical bond between two molecules (in aliquid or acrystal for instance, or between two atoms in amolecule) can be represented by thefollowing simple model. Two particles exhibit competing forces on each other. Theone force is repulsive and rapidly increases with decreasing distance (~1/r13). Theother is attractive and increases less rapidly with decreasing distance (in ionic crystals (~1/r2, between uncharged particles ~1/r7). As aresult of these forces thetwo particles will be located at acertain distance from each other. In Fig.3.1 thepotential energies corresponding to each force and to theresulting net force are drawn schematically. If one particle is located at theorigin of theco-ordinate system, theother will be in theenergy well. Escape from thewell is possible only, if it obtains sufficient kinetic energy to overcome thenet attractive force. This energy is called the binding energy of theparticle. Asimple example is theheat of evaporation. Although theparticle is in theenergy well, it is not at thebottom of thewell, even at thezero point of theabsolute temperature scale (273.15C). All particles have three modes of motion: translation, i.e. displacement of themolecule as awhole, vibrations of theatoms in themolecule with respect to each other, and rotations of themolecule around certain molecular axes. In theenergy well representation: theparticle is not at thebottom of thewell, but at acertain (energy) level above thezero energy. In Fig.3.1 an energy level is indicated by ahorizontal line. Thehigher thetemperature of thesubstance, thehigher energy level will be occupied by theparticle. Theenergy required to leave thewell i.e. to become separated from theother particle is indicated as thebinding energy EB, whereas EB is thebinding energy for therare (heavy) particle. Theenergy of acertain particle at acertain temperature depends on its mass. Theheavier isotopic particle is situated deeper in theenergy well than thelighter (heavy line in Fig.3.1) and, 24

Fig. 3.1. Schematic representation of the potential energy distribution caused by the repulsive and attractive forces between two particles, in this case between oppositely charged ions. The resulting potential is well-shaped (solid line). Theone particle is situated at the origin (r=0). The second particle is situated in the well. The small horizontal lines in the well are theenergy levels of thesystem, thethin and heavy lines referring to thelight and theheavy isotopic particle, respectively. The arrows indicate the respective binding energies at thezero temperature T0 and ahigher temperature T, respectively. At higher temperatures thedifference between the binding energies for the isotopic particles is smaller, resulting in asmaller isotope effect.

therefore, escapes less easily: theheavier isotopic particle (atom or molecule) generally has ahigher binding energy: EB > EB (Fig.3.2: normal case). Examples of this phenomenon are: (1) 1H218O and 1H2H16O have lower vapour pressures than 1H216O; they also evaporate less easily and (2) in most chemical reactions thelight isotopic species reacts faster than theheavy. For example Ca12CO3 dissolves faster in an acid solution than does Ca13CO3. In an isotope equilibrium between two chemical compounds theheavy isotope is generally concentrated in thecompound which has thelargest molecular weight. Thedepth of theenergy well may also depend on theparticle masses in amore complicated manner. Under certain conditions with poly-atomic molecules thepotential energy well is deeper for thelight than for theheavy isotopic molecule. Due principally to this phenomenon thebinding energy of theheavy molecule can be smaller.

1) 2)

H218O et 1H2H16O ont des pressions de vapeur plus faibles que 1H216O; ils svaporent donc moins facilement, et

dans la plupart des ractions chimiques, les espces isotopes lgers ragissent plus vite que abundance and fractionation of stable isotopes celles isotopes lourds. Par exemple, Ca12CO3 se dissous plus vite dans une solution acide que ne Fig.3.2 Reprsentation schmatique de leffet isotopique normal ( gauche) et le fait Ca13CO3. Because theisotope effects discussed above genIf we are dealing with changes in isotopic Pour quelques interactions, le creux dnergie potentielle pour les Lors de lquilibre isotopique entre deux composs chimiques, lisotope lourd est gnralement composition, instance C isque oxidised to les particules lg erally result in lower vapour pressure for theiso(ligne paisse) for est moins profond celui pour concentr dans le compos qui aspecies le poids ( molculaire le plus effect lev.), CO2, thecarbon isotope spcifiques, fractionation refers de liaison pou topically heavy normal isotope Dpendant dinteractions lnergie 13 13 thenew R (CO ) value to theold R (C), in this effect is referred to as the inverse isotope ef 2 La profondeur du puits dnergie peut aussi dpendre de la masse des particules dune faon beaucoup isotopiquement 13 lourde 13 peut tre 13plus importante (ct gauche: effet norm other words a = R (CO )/ R(C). fect (Fig.3.2). Practical examples of theinverse 2 plus complexe. Sous certaines conditions, si lon considre les molcules poly-atomiques, le creux (ct droit: effet inverse) que pour une particule lgre. isotope effect are thehigher vapour pressure of dnergie potentielle est plus profond pour les molcules lgres que pour les molcules lourdes. Et 13 CO2 in theliquid phase as well as thelower solIn general effects simplement en raison de ce phnomne, lnergie de liaison des molcules lourdesisotope peut tre plus are small: 1. ubility of 13CO2 in water than of 12CO2, both at Therefore, thedeviation of from 1 is widely faible. Parce que les effets isotopiques discuts plus haut produisent gnralement des pressions de En gnral, les effets isotopiques sont faibles: 1. Ainsi, une dviation d p room temperature [19]. used rather than the fractionation factor . This vapeur plus faibles pour les espces isotopiquement lourdescouramment (effet isotopique normal ), cet effet est de fractionnement. Cette quantit, qu utilise plutt que le facteur quantity, to which we refer as thefractionAt high temperatures between rapprocher de leffet isotopique inverse thedifferences (Fig.3.2). Des exemples pratiquesation de leffet isotopique fractionnement , est par: by:inverse , dfinie is defined 13 binding energies of isotopic molecules becomes sont la pression de vapeur leve de CO2 dans la phase liquide ainsi que la plus faible solubilit de R smaller, resulting in smaller an ultimately dis13 3 3 CO2 par rapport 12CO2, les deux processus se produisant temprature (Vogel et (10 ) (3.5) B/A ambiante = B/A 1 = B 1 al., (10 ) appearing isotope effects (Fig.3.1). R A 1970).

enrichissement represents ( > 0) or the reprsente l (enrichment > 0) ouse lappauvrissement (de< 0) de lisotope rare Aux tempratures leves, la diffrence entre les nergies de liaison des molcules the isotopiques 3.3. Kinetic and equilibrium pletion ( < 0) of therare isotope in B with rduit, provoquant des effets isotopiques moindres, et disparaissant en phase (Fig.3.1). et sont quivalents (B) et (B). Dans un processus irrv Les symboles ultime B/A B/A A A isotope fractionation respect to A. Thesymbols B/Aand B/A are est le changement de composition isotopique; en dautres termes: la nouvelle comp equivalent to A(B) and A(B). In theone-way Theprocess of isotope fractionation is math- compare lancienne. 3.3 FRACTIONNEMENTS ISOTOPIQUES CINETIQUE ET A LEQUILIBRE process (A B) is thechange in isotopic ematically described by comparing theisotope

other thenew isotopic Parce dcrit que composition, estcomparaison un nombrein petit, il words: est gnralement donn en (pour mille, Le processusratios de fractionnement isotopique est en des rapports of thetwo compounds inmathmatiquement chemical equilibcomposition compared to theold. un en , comme de nombreux auteurs le procla Notons nous ne dfinissons isotopiques de deux composs en quilibre chimique (Abefore B) ou deque deux composs avant et pas aprs rium (A B) or of thecompounds and Because puisquils is isotopique asmall number, it isle generally aphysical transition process ne le font pas rellement ajoutent symbole ). Une valeur de processus de after transition physiqueor ou chemical chimique (A B). Le facteur de fractionnement est toujours 3 given in (per mill, equivalent to 10 ). Note (A B). The isotope fractionation factor is then quations mathmatique alors dfini comme le rapport de deux rapports isotopiques 5 est gale 0.005. La consquence est que, dans les

that we do not define in , as many authors defined as theratio of thetwo isotope ratios: dutiliser /103 la place du simple . Ltudiant doit se souvenir que est un peti claim they do. (In fact they do not, as they alR(B) RB quations, tre numriquement " 25 " of, la place de " 25/103 ". (3.4) il doit ways add the symbol). An value for in= A (B) = B/A = (3.4) crit R(A) RA stance, 5 is equal to 0.005. Theconsequence Le fractionnement de B par rapport A est toujours not B/A ou A(B). De cette d is that in mathematical equations it is incorrect which expresses theisotope ratio incompos thephase or rapport dduisons simplement: qui exprime le rapport isotopique de la phase ou le B par celui de3 la phase ou to use /10 instead of du merely . Thestudent compound B relative to that in A.
compos A. Si nous considrons les changements de composition isotopique, par exemple C oxyd en CO2, le fractionnement isotopique du carbone rapporte la nouvelle valeur 13R(CO2) la valeur

ancienne 13R(C), ou, en dautres termes : 13 = 13R(CO2)/13R(C).

34

Fig. 3.2. Schematic representation of thenormal (left) and theinverse (right) isotope effect. For some interactions thepotential energy well for theheavy particle (heavy line) is less deep than for thelight particle (thin line). Depending on thespecific interaction thebinding energy for theisotopically heavy particle can be larger (lefthand side: normal effect) or smaller (right-hand side: inverse effect) than for thelight particle.

25

INTRODUCTION

[22]. In practice, however, these data are often not known in sufficient detail. With kinetic isotope effects we are confronted with an additional difficulty which arises from the fact that natural processes are often not purely kinetic or irreversAgain, thefractionation of B with respect to Ais ible. Moreover, kinetic fractionation is difficult 3 denoted by B/Aor A(B). FromChapitre thedefinition of to measure in thelaboratory, because (i) comwe simply derive: plete irreversibility can not be guaranteed (part A/B of thewater vapour will return to theliquid), nor (3.6) B/A = A/B (3.6) 1 + A/B can the degree of irreversibility be quantified; (ii) thevanishing phase or compound will have thelast step because in natural processes the anon-homogeneous and often immeasurable isoen dernire tape, puisque dans les processus naturels, les valeurs de sont faibles. values are small. topic composition, because theisotope effect ocIl est important de distinguer entre deux sortes de fractionnement isotopique: le fractionnement It is important to distinguish between two kinds curs at thesurface of thecompound. For example cintique et of le isotope fractionnement lquilibre. fractionnement provient de of processus fractionation: kinetic Le fractionation and cintique thesurface layer an evaporating water mass 18 chimique et equilibrium physique irrversibles, i.e. en sens unique . Cest, par exemple, lvaporation de in leau fractionation. Kinetic fractionation may become enriched O and 2H if themixing avec un loignement immdiat de la vapeur, labsorption et la diffusion des gaz, ainsi que dautres results from irreversible i.e. one-way physical or within thewater mass is not rapid enough to keep chemicalirrversibles processes. Examples theevap- bactrienne its content homogeneous ractions chimiques telles que include la dcomposition des plantes ou throughout. la oration of water with immediate withdrawal of prcipitation rapide de calcite. Ces effets de fractionnement sont premirement dtermins par les Isotope fractionation processes in nature which thevapour from further contact with thewater; nergies de liaison des composs originaux (Part.3.2) dans lesquels, lors des processus physiques, des are not purely kinetic (i.e. one-way processes) theabsorption and diffusion of gases, and such irmolcules isotopiquement lgres ont des vitesses plus importantes et de be plus faibles nergies de will referred to as non-equilibrium fractionreversible chemical reactions as thebacterial deliaison ; pendant les processus chimiques, les molcules lgres ragissent plus rapidement que les ations. An example is theevaporation of ocean or cay of plants or rapid calcite precipitation. These fresh surface water bodies: molcules lourdes. Dans quelques cas toutefois, cest linverse. Cet effet isotopique cintique inverse theevaporation is not fractionation effects are primarily determined by aone-way process (certainly se produit plus communment dans of les theoriginal ractions impliquant des atomes dhydrogne (Bigeleisen et water vapour conthebinding energies compounds denses), neither an equilibrium process as there is (Sect.3.2) in that during physical processes isoWolfsberg, 1958). anet evaporation. topically lighter molecules have higher velociLe second type de fractionnement est le fractionnement lquilibre (ou thermodynamique). Cest ties and smaller binding energies; in chemical Equilibrium fractionation, on theother hand, can essentiellement cet effet est impliqu dansrapidly les ractions lquilibre (ou ractions processes lightqui molecules react more than be determined by laboratory experiments and thermodynamiques). Comme exemple formel, nous avons choisi les ractions dchanges isotopiques: theheavy. In some cases, however, theopposite in several cases reasonable agreement has been is true. This inverse kinetic isotope effect occurs shown between experimental data and thermodymost commonly *A +B A + *B in reactions involving hydrogen namic calculations.(3.7) atoms [20]. Thegeneral condition dans lesquelles lastrisque indique la prsence de lisotope rare. Le facteur de fractionnement pourfor cet theestablishment of Thesecond type of fractionation is equilibrium isotopic equilibrium between two compounds is quilibre entre phases ou composs A et B est la constante dquilibre pour lquation dchange 3.7: (or thermodynamic) fractionation. This is essentheexistence of an isotope exchange mechanism. tially theisotope effect involved in a(thermodyThis can be areversible chemical equilibrium [Aequilibrium ] [*B] [*Breaction. ] /[B] R namic) B aformal examK= = = As = B/ A (3.8) such as: ple we choose reaction: [*A ] [B] theisotope [*A] /[A] exchange RA is to be reminded that is asmall number; in equations one may numerically write, for instance, 25 instead of 25/103. *A + B A + *B (3.7) et molcules 2 2 2 Si des informations suffisantes sur les nergies de liaison des atomes sont disponibles, les (3.9a) where theasterisk points thepresence of fractionnements peuvent tre calculs, aussito bien pour leffet cintique (Bigeleisen, 1952) que pour therare isotope. Thefractionation factor this ne sont or such areversible physical leffet lquilibre (Urey, 1947). En pratique toutefois, ces for donnes pas souvent connues avec process as evaporaequilibrium between phases or compounds Aand tion/condensation: suffisamment de dtails. Avec les effets isotopiques cintiques, nous sommes confronts une B is theequilibrium constant for theexchange redifficult supplmentaire qui provient du fait que les processus naturels ne sont jamais purement action of Eq.3.7: 18 H216O(vapeur) +H 2 O(liquide) cintiques ou irrversibles. De plus, le fractionnement cintique est difficile mesurer en laboratoire, 18 H2 O(vapeur) + H216O(liquide) (3.9b) parce que (i) la complte irrversibilit ne peut [A] [*B] [*B] /[B] RB pas tre garantie (une partie de la vapeur deau va = B/A (3.8) Kla =phase liquide), = pas plus que = peut Thereaction rates of exchange processes and, retourner vers de cette irrversibilit; (ii) [*A] [B] [*A] /[A] ne RA tre quantifi le degr consequently,et theperiods la phase ou le compos qui disparat aura une composition isotopique non-homogne souvent non- of time required to reachPar isotopic equilibrium, If sufficient about the binding mesurable parce que leffet information isotopique se produit la surface deen ce- compos. exemple, la pellicule vary greatly. For instance, theexchange of H la O CO2 proceeds on ergies of atoms and molecules is available, 18 2 de surface dune masse deau qui svapore peut senrichir en O et H si le mlange interne de 2 ascale of minutes to hours at room temperature, thefractionation effect can be calculated, thekimasse deau nest pas assez rapide pour conserver sa composition isotopique homogne durant tout le netic effect [21] as well as theequilibrium effect while that of H2O SO2 requires millennia. processus.
Les processus de fractionnement isotopique dans la nature, qui ne sont pas purement cintiques (i.e. 26 processus univoque) appartiendront la catgorie des fractionnements hors quilibre). Cest, par 36

H 16O + C18O16O H C18O16O H 18O + C16O

r'

k'[H CO 3 ]

A lquilibre isotopique, le bilan des effets isotopiques, en dautres termes:

R( CO R(CO 2 ) abundance and fractionation of stable 3 ) = isotopes

de telle manire qu en combinant les rsultats des Eqs.3.11 et 3.13:

13

13

so that combining Eqs.3.11 and 3.13 results in: Thefractionation resulting from kinetic isotope effects generally exceeds that from equilib 13 k ' [13 CO 2 ][H12 CO 3 ] R(CO 2 ) = 13 = = e rium processes. Moreover, in akinetic process 12 13 k R(HCO 3 ) [ CO 2 ][H CO 3 ] thecompound formed may be depleted in therare (3.15) isotope while it is enriched in theequivalent ce qui que le fractionnement isotopique lquilibre e est quivalent equilibrium process. This can be understood bymontre which shows that theisotopic equilibrium fracdquilibre de la raction dchange isotopique: comparing thefractionation factor in areversible tionation e is equivalent to theequilibrium conequilibrium with thekinetic fractionation factors stant oftheisotope exchange reaction: involved in thetwo opposed single reactions. As H13 CO 3 + 12 CO 2 H12 CO 3 + 13 CO 2 an example we take thecarbonic acid equilibrium 12 12 13 H13CO 3+ CO2H CO3+ CO2 (3.16) of Eq.3.9a: La plupart des valeurs de k et k' sont infrieures 1 de plus de un pour cent. Les Most k and k values are less than 1 by more + CO2+H2OH +HCO! leurs rapports sont moindres de lordre de quelques pour mille -. Plus loin, n than one per cent. Differences between their ra18 O de la vapeur deau lvaporationtios de leau peut provoquer un appauvrissement en For thesingle reactions are less in theorder of several per mill. fois suprieur celui de la vapeur en quilibre avec leau. Ceci est du Later we will see that rapid evaporation of water au fait que la mo 12 CO2+H2OH++H12CO 3 galement favorise dans le processusvapour de condensation. might cause thewater to be about twice as and depleted in 18O as thevapour in equilibrium with En considrant l Eq.3.15, il est vident que, alors que k dune phase de transition thewater. Thereason for this is, that H216O is fa13 CO2+H2OH++H13CO 3 petit que 1, e peut tre suprieur 1. On a un exemple dans le systme CO2 dis voured also in thecondensation process. teneur en13C du CO2 retir rapidement dune solution CO2 aqueux est infrieur thereaction rates are, respectively: From Eq. 3.15 it is obvious that, while k for acertain phase transition is smaller than 1, e 12 r=12k[12CO2]et13r=13k[13CO2] (3.10) might be larger than 1. An example is to be found 38 Chapitre 3 constants. rate where 12k and 13k are thereaction in thesystem: dissolved/gaseous CO2: the13C Chapitre 3 Theisotope ratio of thebicarbonate formed content of CO2 rapidly withdrawn from an aque(HCO!) is: 13 13 13 ous CO2 solution is smaller than that of thedisk[ CO 2 ] r 13 13 R(HCO 3 ) = 12 = 12 = k R(CO 2 ) (3.11) solved CO2 (i.e. 12 C moves faster: k<1), while 13 12 13 13 r k k[ [ CO CO22] ] r 13 13 R(HCO 3 ) = 12 = 12 12 = k R(CO 2 ) under equilibrium (3.11) conditions thegaseous CO2 r k[ CO 2 ] contains relatively more 13C (e>1; inverse isode fractionnement cintique pour cette raction. A linverse, pour: Sect.3.2). ou k est le facteur (3.11) tope effect,
ou k est le facteur de fractionnement cintique pour cette raction. A linverse, pour:

et

fractionation factor for this where k is thekinetic H + + H12 CO 3 12 CO 2 + H 2 O reaction. Conversely, for: H + + H12 CO 3 12 CO 2 + H 2 O 12 H++H12CO 3 CO2+H2O and + 13 13 H+ + H13 CO3 13 CO 2 + H 2 O H +H CO CO2+H2O 3 H + + H13 CO 3 13 CO 2 + H 2 O

3.4. Theoretical background of equilibrium fractionation

In this section we will present adiscussion of theorigin of isotope effects, in particular themass-dependent isotope fractionation, based on some principles from thermodynamics and les taux de raction sont rates are thereaction statistical mechanics. Thetreatment here will not les taux de raction sont be exhaustive and so, for full details, thereader 12 12 12 12 13 = 12 k '[ H12 CO3 ] 13r= et 13k[H1313 r' = [ H 13CO3 ]is referred to textbooks (3.12)on these subjects. Abasic r'= [H CO CO 3]et 3] k '(3.12) 12 12 12 13 13 13 r ' = k '[ H CO3 ] et r ' = k '[ H CO ] (3.12) Thecarbon dioxide formed (CO ) has an iso- 3 discussion has been given by [23, 24].
et

Abasic principle of quantum physics is that theenergy of theparticle can take only certain 13 ] r' 13 k'[H13CO 3 ' 13 13 discrete values. This is true for any kind of moR(CO 2 ) = 12 = 13 = k R(HCO 3 ) (3.13) 13 13 r' k' CO k'[H [H12 CO3 ] r' 12 13 ' 13 tion. These discrete energy values were already 3] R(CO 2 ) = 12 = 12 = k R(HCO 3 ) (3.13) r' k'[H12 CO 3 ] mentioned in Sect. 3.2, where we discussed A lquilibre (3.13) isotopique, le bilan des effets isotopiques, en dautres termes: theposition of aparticle at acertain time at acertain level in theenergy well (Figs.3.1 and 3.2). A lquilibre isotopique, le bilan des effets isotopiques, en dautres termes: At isotopic equilibrium theisotope effects bal13 R(CO 3 ) = 13 R(CO 2 ) Abasic principle (3.14) of statistical mechanics states ance, in other words: 13 13 R(CO 3 ) = R(CO 2 ) (3.14) that thechance that aparticle is at acertain en13 qu en 13 de telle manire combinant les rsultats des Eqs.3.11 et 3.13: ergy level r is: R(CO3)= R(CO2) (3.14)
Le gaz carbonique form (CO2) a un rapport isotopique: de telle manire qu en combinant les rsultats des Eqs.3.11 et 3.13:
13 k ' [13 CO 2 ][H12 CO 3 ] R(CO 2 ) = 1313 = = e 13 12 12 13 [ CO CO22 ][H ][H CO CO33 ] ] (CO 23)) [ k ' (HCO RR = = = e k 13 R(HCO 3 ) [12 CO 2 ][H13 CO 3 ]

Le gaz carbonique form (CO2) a un rapport isotopique:

tope ratio

(3.15) (3.15)

27

ce qui montre que le fractionnement isotopique lquilibre e est quivalent la constante dquilibre de la raction dchange isotopique: ce qui montre que le fractionnement isotopique lquilibre est quivalent la constante

* q Bnergies *q /q q Ces seulement que certaines valeurs discrtes. Ceci est vrai pour nimporte quel dplacement. B) = K =ne Apeut = B B A( Un principe de base de la physique quantique stipule que lnergie des particules prendre Un principe de base de la physique quantique stipule que lnergie des particules ne peut prendre * qA / qA q A qB dune discrtes ont dj t mentionnes dans la partie 3.2, o nous avons discut de la *position * q Bnergies * qB / qB q A Ces seulement que certaines valeurs discrtes. Ceci est vrai pour nimporte quel dplacement. seulement que certaines valeurs discrtes. Ceci est vrai pour nimporte quel dplacement. Ces nergies ( B ) = K = = particule un instant donn et un certain niveau dans le creux dnergie (Figs.3.1 et 3.2). A discrtes ont dj t mentionnes dans la partie 3.2, o nous avons discut de la * position dune * q A / q A fonctions de rpartition. q q A les B diffrentes Nous devons discrtes ont dj t mentionnes dans la partie 3.2, o nous avons maintenant discut de valuer la position dune Un principe base donn des tats mcanique est que la chance quune particule unde instant et de un la certain niveau statistique dans le creux dnergie (Figs.3.1 et 3.2). particule se INTRODUCTION particule un instant donn et un certain niveau dans le creux dnergie (Figs.3.1 et 3.2). Dans la Part.3.2, les trois modesles dediffrentes dplacement sont nomms translation, rotation Nous devons maintenant valuer fonctions de rpartition. est: trouve un niveau dnergie donn Un principe de base des tats de la rmcanique statistique est que la chance quune particule se dunparticule systme Un principe de base des tats de la mcanique statistiquefonction est que de la partition chancetotale quune seun compos ou une phase est en relation a Dans la Part.3.2, les trois modes de dplacement sont nomms translation, rotation trouve un niveau dnergie donn r est: /kT de partition des diffrents dplacements par: themolecule around molecular axes, and interr trouve un niveau e dnergie donn r est: fonction de partition totale dun systme un compos une phase est en relation a pr = molecular (external) motions, such as ou vibrations q r /kT de partition des diffrents dplacements par: e r /kT q = qtrans qrotqvibr of molecules with respect to each and rotations

La fonction de partition est donc la sommation de la population de tous les dnergies pour un allons brivement mentionner les divers temprature surniveaux le fractionnement, nous La fonction de partition est donc la sommation de la population tous les niveaux dnergies pour un que les considrations thermodynamiques montrent que les de conditions dquilibre peuvent tre of thepopulation of all energy levels of acerTranslation of amolecule as awhole has theparsystme donn, et dtermine ainsi ltat dnergie dudit systme. Cest une donne importante, parce La translation dune molcule dans son ensemble a la fonction de partition suivante: partition. systme donn, et dtermine ainsi ltat dnergie dudit systme. Cest une donne importante, parce exprimes entain tant system que rapport des fonctions de partition. and so determines the energy state of tition function: peuvent tre que les considrations thermodynamiques montrent que les conditions dquilibre que les considrations thermodynamiques montrent que conditions dquilibre peuvent tre thesystem. It is an important quantity, because 3 Lales translation dune molcule dans son ensemble a la fonction de partition suivante: exprimes en encore tant que des fonctions de partition. Considrons larapport raction dchange isotopique de l Eq.3.7: 2 exprimes enthermodynamic tant que rapport des fonctions de partition. mkT 2 considerations show that equiqtrans = V (3.20) 2 Considrons encore laconditions raction dchange laratio Eq.3.7: of librium can be isotopique expressedde as h 3 Considrons *A encore raction + B la A + *Bdchange isotopique de l Eq.3.7: 2mkT 2

pr = e pr = k q is theBoltzmann constant and T theabother, in acrystal lattice, for instance. Most syswhere q Boltzmann et T la temprature absolue du compos. ou k est la constante de La valeur q, la fonction q =q qrottoo qvibrde trans Chaque fonction de partition rsulte de mouvements intramolculaire solute temperature of thecompound. Thevalue of tems are complicated to allow an exact cal- (interne), tels l de partition, est dtermine par lobligation que la somme de toutes les chances soit gale lunit : atomes les uns par aux les rotations de la molcule q, thepartition function is determined by thereou k est la constante de Boltzmann et T ,la temprature absolue du compos. Larapport valeur de q,autres, la fonction culation of thepartition functions. Theonly sim-autour de laxe mo ou k est la constante de Boltzmann et T la temprature absolue du compos. valeur dersulte q, la fonction Chaque fonction La de partition de mouvements intramolculaire (interne), tels l quirement that thesum of all chances mouvements intermolculaires (externes) telles les rotations et les vibrations des mo ple systems are ideal mono-atomic or di-atomic de partition, est dtermine par lobligation que la somme de toutes les chances soit gale lunit : dtermine par lobligation que la somme de toutes les chances soit gale lunit : de partition, est atomes les uns par rapport aux autres, les rotations de la molcule autour de laxe mo gases. Thetranslations are not hindered by neighpar rapport aux autres, dans un treillis cristallin, par exemple ; La plupart des sys pr = 1 equals unity: mouvements bouring intermolculaires (externes) telles les intermolecular rotations et les vibrations des mo =0 r atomsun or molecules and compliqus pour permettre calcul exact des fonctions de partition. Les gaz id p = 1 par rapport aux autres, dans un treillis cristallin, par exemple ; La plupart des sys and rotations do not exist, so that only prr = 1 diatomiques, vibrations reprsentent les seuls sytmes simples. Les translations ne sont pas gne =0 r donc que : r =0 compliqus pour permettrecomponents un calcul exact des fonctions de partition. Les gaz id theinternal of funcou les molcules voisins et les vibrations et thepartition les rotations intermolculaires nexist diatomiques, tions reprsentent lesbe seuls sytmes simples. Les translations ne sont pas gne have to calculated. In order to point out /kT donc que : so manire que seul les composants internes doivent tre calculs. that: e r (3.17) donc que : q = themass dependence of fractionation factors and ou les molcules voisins et les vibrations et les rotations intermolculaires nexist r =0 r /kT Afin de montrer la dpendance des facteurs de fractionnement et pour illustrer l to illustrate the influence of temperature on frac q = e r /kT (3.17) doivent tre calculs. manire (3.17) que seul les composants internes q partition =r e est donc la sommation de la population (3.17) =0 La fonction de de tous les niveaux dnergies pour unallonsthevarious temprature sur le fractionnement, nous brivement mentionner les divers tionation, we will briefly mention parti r =0 Afin deCest montrer la dpendance des parce facteurs de fractionnement et pour illustrer l tion systme donn, et dtermine function ainsi ltatis dnergie dudit systme. une functions. donne importante, partition. Thepartition thus thesumming up

(V=volume in which themolecules are free to h les *A + B A + *B (V = volume dans lequel molcules sont mouvoir, m est la masse de *A + B again A + *B Consider theisotope exchange of HCO outhemass deux phases du libres de se ou A et B reprsentent deux composs diffrents (parreaction exemple, CO2 et 3 ) is move, m of themolecule, h Plancks constante de Planck). Dans un gaz, la contribution du mouvement au rapport de la fonc Eq.3.7: mme compos (par exemple, H2O liquide et vapeur deau),(V et = lastrisque se rapporte la prsence de libres de contribution constant). In deux agas thetranslational volume lequel molcules sont se mouvoir, m est la masse de HCO phases du ou A et B reprsentent deux composs diffrents (par exemple, CO 2 etdans 3 ) oules 2 est alors (M poids molculaire): et HCO ) fractionnement ou deux phases-i.e. du ou A et B reprsentent deux composs (par la exemple, CO 2= 3 H, etc.). Dans dfinition du facteur de lisotope rare dans la molcule (13C, 18O, diffrents to thepartition function ratio ismouvement (M=molar constante de Planck). Dans un gaz, la contribution du au rapport de la fonc mme compos (par exemple, H2O liquide et vapeur deau), et lastrisque se rapporte la prsence de then *A + B A + *B mme compos (par exemple, H13 et vapeur deau), et lastrisque se rapporte la prsence de 2O liquide 3 3 weight): la constante dquilibreles concentrations, ou plutt les activits, sont donc reprsentes par des 18 2 est alors (M poids du= facteur de fractionnement -i.e. 2 lisotope rare dans la molcule ( 13C, 18O, 2H, etc.). Dans la dfinition * q molculaire): 3 *m 2 3 *M H,different etc.). Dans la dfinition du facteur de fractionnement -i.e. lisotope dans laAand molcule ( C, O, fonctions rare de partition: denote two compounds = = 3 2 la constante where dquilibrelesBconcentrations, ou plutt les activits, sont donc reprsentes par des 2 3 * * * q m M qdonc la constante (for dquilibrelesCO concentrations, ou plutt les activits, sont reprsentes = Mdes m 2 par instance, trans 2 and HCO 3 ) or two phases of (3.21) = * q *M 2 *m fonctions de partition: fonctions de thesame partition: compound (for instance, liquid H2O and = = q m M trans qui est dpendante la temprature. M 39 m q de trans water vapour), and theasterisk refers to thepres2

partition functions.

qtrans =

that r0 is themoment of inertia of arotating mass, and that s=1, unless themolecule consists (3.19) of two equal atoms in which s=2. In agas de la rotation gaux, cas pour lequel s est gal 2. Dans case un gaz, la contribution therotational Chaque fonction de partition rsulte de mouvements intramolculaire vibrations des to thepartition funcpartition donc : tels les contribution (3.19) est(interne), q=q transqrotqvibr tion ratio thus is: atomes les uns par rapport aux autres, les rotations de la molcule autour de laxe molculaire, et les partition function results intramolecmouvements Each intermolculaires (externes) telles from les rotations et les vibrations molcules * q des * * m1 les Munes s (3.23) = = ular (internal) motions, such as vibrations of at q des par rapport aux autres, dans un treillis cristallin, par exemple ; La plupart systmes sont trop m * M * s 1 rot oms with respect to each other, and rotations of compound or one phase is related to thepartition q = qtransqrotof qvibr functions thedifferent motions by:

o entre deux atomes et la masse rduite de la molcu ou ro est la distance dquilibre masse la place de m1atoms et m2 autour deis chacun deux. Nous devons thetwo and thereduced mass of de plus rappele We must now evaluate thevarious partition funcmrpartition. 2); lnergie de rotation est gale celle dun systme dans lequel tourne autour Nous devons maintenant valuer les diffrentes fonctions de moment dinertie dune masse en rotation, et que s = 1, sauf si la themolecule= m1m2/(m1 + m2); theenergy of ro-molcule consiste tions. masse la place de m1 et m2 autour de chacun deux. Nous devons de plus rappele tationrotation is equal that of. asystem where rotates Dans la Part.3.2, les trois modes de dplacement sont nomms translation, etto vibration La 40 moment dune masse enof rotation, et que s of = 1, si la molcule consiste In Sect. 3.2 thethree modes of motion were dinertie around thecentre mass instead msauf 1 and m2 fonction de partition totale dun systme un compos ou une phase est en relation avec les fonctions mentioned, translation, rotation and vibration. around each other. We should further remember de partition des diffrents dplacements par: of asystem40 Thetotal partition function of one 2 Fractionnement en isotopes stables

C, 18O, de ence of arare isotope in themolecule (13 which is temperature independent. La partition le mouvement 39 de rotation interne dune molcule diatom quifonction est dpendante de la pour temprature. 2 39 H, etc.). In thedefinition of thefractionation facThepartition function for internal rotational motor i.e. theequilibrium constant theconcentraLa fonction de partition 2 pour2le mouvement de rotation interne dune molcule diatom 8 r0 kT molecule is: tion of adiatomic Chapitre tion or rather theactivities are now 3 represented qrot = sh 2 2 by thepartition functions: 8 2 r0 kT (3.22) qrot = q A * qB * qB / qB sh 2 est la distance dquilibre entre deux atomes et la masse rduite de la molcu ou r o (3.18) = A ( B) = K = (3.18) * q A qB * q A / q A de rotation est gale celle dun systme dans lequel m2); lnergie where r is theequilibrium distance between tourne autour

compliqus pour permettre un calcul exact des fonctions de partition. Les gaz idaux, mono ou diatomiques, reprsentent les seuls sytmes simples. Les translations ne sont rare pas gnes par les avec *m1, isotope de latome m1.atomes Ce rapport est galement dpendant de la tempr ou les molcules 28 voisins et les vibrations et les rotations intermolculaires nexistent pas, de telle La fonction de partition de la vibration est: manire que seul les composants internes doivent tre calculs.

e linfluence de la Afin de montrer la dpendance des facteurs de fractionnement et pour qvibr illustrer = e h / kT fonctions de temprature sur le fractionnement, nous allons brivement mentionner les 1diverses

h / 2 kT

Fractionnement en isotopes stables

C ln = C1 + + 3 (3.25) 1 (3.31a) T T2 2 1 2 1 k ' 1 2 masse rduite de la molcule et (3.25) k 'la (3.25)une =1 ou de nouveau est k' est la constante de (3.25) force. Dans 2 = k 1 ' avec lapproximation souvent utilise pour le fractionnement: with theoften used approximation for thefrac2 2 (3.25) = approximation de premier ordre, k' nest pas altr par la substitution dun isotope dans la molcule, et ou de nouveau la masse rduite de la molcule et k' est la constante de force. Dans une 2est tionation: donc: approximation de premier ordre, k' nest pas altr par la themolesubstitution dun dans la molcule, et where again isrduite thereduced mass of C2Dans /T une isotope ln(1+ ) =Dans C 1 + une ou de nouveau est la masse de la molcule et k' est la constante de force. ou de nouveau est la masse rduite de la molcule et k' est la constante de force. ou de nouveau est la masse rduite de la molcule et k' est la constante de force. Dans une culepremier and kordre, is the force constant. In a first order C2/T (3.31b) dans ln(1+ ) = C1 +et donc: approximation de k' nest pas altr par la substitution dun isotope la molcule, approximation de premier 1ordre, k' nest pas altr par la substitution dun isotope dans la molcule, et approximation de premier ordre, k'is nest pas altr par la substitution dun isotope dansmontrer la molcule, et trs hautes tempratures, la contribution de approximation k not altered by an isotope subOn peut de plus qu donc: 2 * inthemolecule, donc: It can further be shown, that at very high tem1 donc: stitution and so: (3.26) des = fractionnement contrebalance le produit facteurs translation et rotation, ce qui fina 2 peratures thevibrational contribution to thefrac * * 1 (3.26) = = 1, et donc les effets isotopiques disparaissent quand les tempratures sont suffisa 1 1 2 tionation balances theproduct of thetranslational * * (3.26) 2 2 (3.26) = * and factors, so that finally at very high = (3.26) (3.26) =normales A partir ce qui rotational prcde, nous pouvons dduire les conclusions suivantes: Aux tempratures dude dnominateur dans lEq..3.24 peut (T < hv/k), la fonction exponentielle * ** temperatures = 1, and thus, isotope effects distre nglige. Le rapport de la partition exponentielle est alors: Aux tempratures normales (Tfonction < hv/k), de la fonction du dnominateur dans lEq..3.24 peut 1) Dans un processus cintique la phase ou le compos form appear sufficiently high temperatures. Aux tempratures normales (T < hv/k), la fonction exponentielle du dnominateur dans at lEq..3.24 peut (irrversible), At normal temperatures ( T < hv / k ) theexponentre nglige. Le rapport de la fonction de partition est alors:du dnominateur dans lEq..3.24 peut Aux tempratures normales (T < hv/k), la fonction exponentielle lourds pardans rapport la phase ou au compos originel (k < 1); les prdic Aux normales (T < hv/k), la fonction exponentielle du dnominateur lEq..3.24 peut tre tempratures nglige.tial Le rapport de lain fonction de partition est in alors: function thedenominator Eq.3.24 isotopes can From theforegoing we can draw thefollowing *q ( fonction * ) / 2 kT de partition est alors: tre nglige.Le rapport de h la de fractionnement ne peuvent tre que qualitatives (un corps deau = de (3.27) e la Thepartition function ratio then sur is: le degr tre nglige.be Leneglected. rapport fonction de partition est alors: conclusions: 18 vibr * *q q h ( * ) / 2 kT q rapide sera appauvri en O relativement leau elle-mme) ; h ( * ) / 2 kT (3.27) = e (3.27) = e h ( * ) / 2 kT *q q (1) In akinetic (one-way or irreversible) process q (3.27) (3.27) = e vibr * q vibr h ( * ) / 2 kT 2) Dans un processus dquilibre isotopique (rversible), on ne peut q (3.27) ou, en insrant thephase or compound formed is depleted in pas prdire avec vibr = e lEq.3.26: q vibr phase (ou un theheavy compos) sera enrichie ourespect appauvrie isotopes lourds. Toutefois isotope with to en theorigiou, lEq.3.26: ou,en eninsrant insrant lEq.3.26: or, inserting Eq.3.26: ou, en insrant lEq.3.26: (liquide plutt que vapeur) ou le compos ayant la masse molculaire la plus im < 1); theoretical nal phase or compound ( k h *q ou, en insrant lEq.3.26: = (3.28) exp 1 predictions about thedegree fractionation vs CO2) contient normalement labondance la of plus importante disotopes lourds. * q h2 * *q q h 1 * (3.28) exp vibr = q h kT can only be qualitative (fast evaporating wa = (3.28) exp 1 (3.28) q kT = exp * * (3.28) et en 18 3) En conditions dquilibre supposant que des donnes spectroscopiques su 1 vibr 2 q 2kT q 2 kT * O relative to thewater itter is depleted in vibr * vibr q h + m2 = (3.28) e peut tre calcule; les mesures de e de 1 nergies de liaison sont disponibles, ). exp avec = m1m 2(m self) 1 q1 kT + * +vibr m avec = m1m 2(m 22 where 2). = m1m (m 1 m2). sont reportes dans le chapitre 6. (m + m avec = m m avec = m 1 2(m 2). 1m2 11 + 2). (2) normales In an isotopic equilibrium (reversible) proLe rapport de la fonction de partition dun gaz diatomique aux tempratures est alors obtenu Le rapport de la fonction de partition dun gaz diatomique aux tempratures normales est alors obtenu Thepartition function ratio of adi-atomic gas at rgle 4) En gnrale, le fractionnement dcrot avec laugmentation des temp cess it can not with certainty be predicted Le rapport de la fonction de partition dun gaz diatomique aux tempratures normales est alors obtenu en combinant les quations 3.19, 3.21, 3.23 et 3.28: Le de la fonction partition dun gaz diatomique aux tempratures normales est alors obtenu m (m avec = m1 2 1 + m2). de enrapport combinant les quations 3.19, 3.21, 3.23 et 3.28: normal temperatures is thus obtained by combinChapitre 3 whether theone phase or compound is enen combinant les quations 3.19, 3.21, 3.23 et 3.28: montr, par exemple, dans le Chapitre 6, pour les changes lquilibre CO2 en combinanting les Eqs.3.19, quations 3.19, 3.21, 3.23 et 3.28: 3.23 and 3.28: Le rapport de la fonction de 3.21, partition dun gaz diatomique aux tempratures normales est alors obtenu riched or depleted in theheavy isotope. 41 41 1 3.19, 3.21, 3.23 et 3.28: en combinant les quations However, thedense phase (liquid rather than 41 2 41 *q *M *m s h 1 vapour) or thecompound having thelargest exp (3.29) = 42 (3.29) q M m *s * 2kT molecular mass (CaCO 41 3 versus CO2) usually contains thehighest abundance of theheavy where m and *m refer to theexchanging isotopes. o m et *m se rfrent aux isotopes changs. Le facteur de fractionnement lquilibre entre deux isotope Theequilibrium fractionation factor between two gaz diatomiques A et B est donn par lEq.3.18. Il faut noter que, si A ou B consistent en deux atomes (3) Under equilibrium conditions and provided di-atomic B is given Eq.3.18. It ou CO2Aand ), la vritable relation by entre et K contient un facteur 2, tel que ce quivalents (tels que O2 gases sufficient spectroscopic data on the binding should be noted that, if Aor B consists of two facteur 2 provenant de s/*s sannule lorsque lon calcule . Un exemple numrique simple est donn equal atoms (such as in O2 or CO2), thetrue relaenergies are available, e may be calculated; C2 1 ' La dpendance de 2 masse de la frquence de vibration de loscillateur harmonique est donne par: 2 k

1* 1 partition est donc * q: * m1 M s o m et *m sede rfrent aux isotopes changs. Le facteur de fractionnement lqu * = = m partition donc :rare avec m1, est isotope deindependent latome rapport est galement dpendant la temprature. 1. Ce tio of temperature. thefactor 2 arising(3.23) from s/*s is cancelled in cal qalso is m * M * s rot gaz diatomiques A et B est donn par lEq.3.18. Il faut noter que, si A ou B consistent 1 * culating . Asimple numerical example is given avec m1, isotope rare de latome m1. Ce rapport est galement dpendant de la temprature. *partition * m q *de s 1 M La fonction de la vibration est: Thevibrational partition function is: = = * m *q * s ou CO ), la vritable relation entre et K contient un fact quivalents (tels que O2 (3.23) 1 M in Sect.3.7. q m1 * M *est: s = = vibration (3.23) 2 * partition rot de La fonction de de avec m1, isotope rare rapport est galement dpendant de la temprature. 1. Ce h latome / 2la kT m1 m * M * s facteur 2 provenant de s/*s sannule lorsque lon calcule . Un exemple numrique s q rot e Ageneral approximate (3.24) qvibr = hh/2/kT (3.24) expression for thefrac* kT vibration est: dans la partie 3.7. La fonction de partition de la avec m , isotope rare de latome m1. Ce rapport est galement dpendant de la tionation temprature. 1e e factor as afunction of thetemperature is * 1 avec m1, isotope m1. Ce rapport est galement dpendant de la temprature. qvibrrare (3.24) = de latome h / kT obtained from Eqs.3.18 and 3.29: 1 de e h /la 2 kT La fonction partition vibration approximative du facteur de fractionnement en tant que where thefrequency of vibration of Une thetwo o est la de frquence de vibrationest: de deux atomes lun parexpression rapport gnrale lautre. La frquence est e is La fonction de partition de la vibration est: q = (3.24) vibr temprature est obtenue partir des quations hkT respect / kT h /2 with to spectroscopiques each other. Thefrequency gnralement connue donnes exprimentales. Il peut que est la 3.18 et 3.29: B/T tre o est la atoms frquence de vibration de deux atomes lun par rapport lautre. Lamontr frquence 1 par e e (3.30) = A e h / 2 kT q (3.24) = e dehla vibrgenerally is / kT known from experimental specdpendance vis--vis temprature de leffet de fractionnement est du, premire hypothse, gnralement connue donnes spectroscopiques exprimentales. Il en peut montr que la epar = 1 qvibr (3.24) B/T tre / kT vibration de deux atomes lun par rapport o est la troscopic frquence Ae lautre. La frquence A est = data. Thetemperature dependence of 1 e hde where the coefficients B do not depend thermique de vibration. de leffet de fractionnement est du, en premire hypothse, and dpendance vis--vis de lala temprature la o est la thefractionation frquence despectroscopiques deuxbe atomes lun par rapport lautre. La frquence est que la gnralement connue de parvibration donnes Il peut tre montr effect can shown toexprimentales. be caused on temperature but contain all temperature-indeo est la thermique frquence de de la vibration de deux atomes lun par rapport lautre. La frquence est dpendance vibration. o les of coefficients A et B ne dpendent pas de la temprature mais contiennent tou gnralement connue par donnes spectroscopiques exprimentales. Il peut tre montr que la La dpendance de masse de la frquence de vibration de loscillateur harmonique est donne par: primarily by thetemperature dependence dpendance vis--vis de la temprature de leffet de fractionnement est du, en premire hypothse, la pendent quantities (mass, vibration frequency). gnralement connue par donnes spectroscopiques exprimentales. Il peut tre montr que la dpendance vis--vis de la temprature de leffet de fractionnement est du, en premire hypothse, la thermiquement indpendantes (masse, frquence de vibration). Le logarithme natur thevibration. La dpendance de masse frquence de vibration de loscillateur harmonique est donne par: of Thenatural logarithm thefractionation factor dpendance thermique la la vibration. dpendance vis--vis de de la de temprature de leffet de fractionnement est du, en premire hypothse, la dpendance thermique de la 1 vibration. fractionnement est approch par les sries de puissance: is approximated by thepower series: 2 Themass of de thevibration frequency harmonique dpendance thermique la vibration. 1 1 de k 'dependence La dpendance de masse de la frquence vibration de loscillateur est donne par: (3.25) = La dpendance de masse de la frquence de vibration de loscillateur harmonique est donne par: of theharmonic oscillator is given by:

gaux, cas pour lequel s est gal 2. Dans un gaz, la contribution de la rotation la fonction de Chapitre 3 Fractionnement en isotopes stables partition estpour donclequel : gaux, cas s est gal 2. Dans un gaz, la contribution de la rotation la fonction de 1 partition est donc : 2 lam Fractionnement en isotopes stables gaux, cas pour lequel s est gal 2. Dans un gaz, la contribution de la rotation fonction de * q * M s h abundance and fractionation= of stable* isotopes 1 *q * *m s en isotopes exp Fractionnement stables 1 M = = (3.23) partition est donc : q M m *s * 2kT m *q q * *m M M *ss 11 * rot = = (3.23) gaux, cas pour lequel s est gal 2. Dans un gaz, la contribution de la rotation la fonction de

* s est therare m *isotope M * sun of gaux, cas pour gal Dans gaz, la contribution de la rotation la fonction deK contains afactor 2 such that q lequel rot 1 2. m is atom m . This ration between and where

dans la partie 3.7.

Une expression gnrale approximative du facteur de fractionnement en tant que fonction de la temprature est obtenue partir des quations 3.18 et 3.29: = AeB/T (3.30)

29

o les coefficients A et B ne dpendent pas de la temprature mais contiennent toutes les quantits

*M A + MB M A MB *D = D * M AM B M AM B

Dans lexemple de la diffusion de vapeur deau dans lair, le facteur de fractionneme INTRODUCTION loxygne est (MB de lair est considr comme gal 29, MA = 18, *MA = 20):

measurements on e of various isotope equilibria will be reported in chapter 6

18

(4) As arule fractionation decreases with inBy diffusion through airsappauvrie water vapour thus will creasing temperature; in Chapter Par 6 diffusion this dans lair, la vapeur deau donc en 18O (en accord avec les l 18 become depleted in O (in agreement with is shown, for instance, for theexchange fin de la Part.3.4) de 31 given : 18 at = 31 . of Sect.3.4) by 31: therules theend equilibria of CO2 H2O and H2Oliquid 18 =31. en 13C pour la diffusion du CO2 dans lair est: Fractionnement en isotopes stables H2Ovapour. At very high temperatures theisoLe facteur de fractionnement topic differences between thecompounds Chapitre 3 The 13C fractionation factor for diffusion of CO2 disappear. through air is: H2Ovapeur. A trs hautes tempratures, les diffrences isotopiques entre les composs
45 + 29 44 29 2 3.5. Fractionation by diffusion = = 0.9956 (3.36) 29 les + 29 44 composs H2 Ovapeur . A trs hautes tempratures, les diffrences isotopiques entre 45 2 vapeur 3.5 FRACTIONNEMENT DIFFUSION As was mentioned inPAR Sect.3.2 isotope fractiondisparaissent. occur mobili13 113 raison des Comme cela ation a t might mentionn enbecause Part.3.2,of lethedifferent fractionnement isotopique survenir Chapitre 3 of = 4.4, adepletion inpeut other words = 4.4en , correspondant un appauvrissement de 4.4 . en dautres termes ties of isotopic molecules. An example in nature 4.4. mobilits diffrentes des molcules isotopiques. Dans la nature, la diffusion de CO2 ou H2O travers 3.5 FRACTIONNEMENT is thediffusion of CO2PAR or HDIFFUSION 2O through air.
13

20 + 29 18 29 2 = = 0.969 20 29 18 + 29

(3.35)

disparaissent.

Fractionnement Fractionnement en en isotopes isotopes stables stables

lair en est un exemple. 3.6 RELATION ENTRE 1 RAPPORTS ISOTOPIQUES ATOM Comme cela According a t mentionn en Part.3.2, le net fractionnement isotopique peut survenir raison 2 to Ficks law the flux of gas, F, 45 + 29 en 44 29 des 13 Chapitre 3 MOLECULAIRES 3.6. Relation between atomic and Selon la loi de Fick, le flux net de gaz, F, travers une unit de surface, est: = = 0.9956 ou H2 O travers mobilits diffrentes molcules isotopiques. de CO throughdes aunit surface area is: Dans la nature, la diffusion 2 2 29 44 2 + 29isotope 45 molecular ratios Nous devons considrer plus attentivement la signification du rapport isotopique dan 1 lair en est un exemple. 2 + 45 29 44 29 dC 13 We want torares have acloser look themeaning =isotopes = 0.9956 (3.36) labondance des dun lment dansat les molcules poly-atomiques con 13 (3.32) termes F = D (3.32) 29 = 44 4.4 , en + 29 45 correspondant un appauvrissement de 4.4 . Selon la loi de Fick, led flux dedautres surface, est: x net de gaz, F, travers une unitdeux ratio in thecontext of theabunatomes of de theisotope cet lment. Le rapport isotopique correspond la chance que l 13 dance of rare isotopes ofappauvrissement an element in.poly= 4.4 , correspondant un de 4.4 dautres soitenremplac par un isotope rare. Pour tre plus prcis, nous dfinissons le ra where d C /dx is theconcentration gradient in termes d C ou dC/dx est le gradient de concentration dans la direction 3.6 de diffusion et D la constante de diffusion. RELATION ENTRE RAPPORTS ISOTOPIQUES ATOM atomic molecules, containing at least two atoms (3.32) F = D thedirection of diffusion and D is thediffusion ) comme labondance de tous les atomes isotopiquement rares du com atomique (R atom 3.6avec m, RELATION ENTRE Theisotope RAPPORTS ISOTOPIQUES ATOMIQUES ET of element. is thechance dx MOLECULAIRES Cette dernire est proportionnelle la temprature et 1/m, lathis masse molculaire. Cette ratio constant. Thelatter is proportional to thetemperlabondance that de tous les isotopes abondants. Pour plus explicite, nous avons MOLECULAIRES theabundant isotope been tre replaced by proportionnalit rsulte du que toutes les molcules dans un gaz (mlange) ont la mmehas ature and to mfait , where m is themolecular mass. Nous devons considrer plus attentivement la signification du rapport isotopique dan exemple simple, isotopes de lhydrogne dans molcule deau: Nous devons considrer plus attentivement la signification du la rapport isotopique dans le contexte de the rare isotope. To be more specific, we define ou dC/dx est et le donc gradient concentration dans la direction de diffusion et Dles la constante de diffusion. 2 moyen quivalent. La vitesse moyenne des molcules, et donc, leur temprature un de mv This proportionality results from thefact that all labondance the des rares dun lment dans molcules poly-atomiques contenant au moins labondance desisotopes isotopes rares dun lment dans les molcules poly-atomiques con ) as theabundance isotope ratio (les Ratom Cette dernire est proportionnelle la temprature et 1/m, avec m, la atomic masse molculaire. Cette deux atomes de cet lment.2Le 16 rapport correspond la mobilit sont molecules inversement proportionnelles m. equal in agas (mixture) have tempera1 isotopique 2 17 1 2 chance 18 1 que lisotope 2 16abondant 2 deux atomes of de cet lment. Le rapport isotopique correspond la chance que l all rare isotopic atoms in thecompound di[ H O H] + [ H O H] + [ H O H] + 2[ H O H] + ........ 2 par (mlange) proportionnalit du equal fait que toutes les molcules dans un gaz ont la mme 2 soit remplac un = isotope rare. Pour tre plus prcis, nous dfinissons le rapport isotopique R turersulte and thus average mv . Theaverage atom 1 16 1 1 17 1 1 18 1 1 16 1 vided by theabundance of all abundant isotopic remplac un isotope rare. Pour plus prcis, nous dfinissons le ra 2 Si le processus de diffusion implique le quivalent. mouvementLa du vitesse gaz soit A au travers du gaz B,labondance m doit toutefois tre )par comme de tous atomes isotopiquement rares du compos divise atomique (Ratom 2[ H O H] +les 2[ H tre O H] + 2[ H O H] +[ H O par H] + ...... 2 moyen moyenne des molcules, et donc, leur temprature et donc un velocity ofmv themolecules and, thus, their mobiliatoms. For thesake of clarity, we select asimple labondance de tous les isotopes abondants. Pour tre plus explicite, nous avons slectionn un ) comme labondance de tous les atomes isotopiquement rares du com atomique (R atom remplace par la masse rduite: mobilit sont ties inversement proportionnelles m. are inversely proportional to m. exemple simple, les isotopes de lhydrogne dans molcule deau: example, theisotopes of la hydrogen in water: labondance de tous les isotopes abondants. Pour plus 2explicite, avons H218O en nous nominateu Les abondances de second ordre, telles que par tre exemple 2 m 16 doit 1 2 17 1 2 18 1 2 16 2 If de thediffusion process of interest Si le processus diffusion le mouvement du gazinvolves A au travers du gaz B, toutefois tre m A mB implique exemple simple, les isotopes de lhydrogne dans la molcule deau: [ H O H] + [ H O H]ce + [ contexte, H O H] + 2[ O H] + ......... dnominateur, Dans leHrapport isotopique molculaire 2 ont t Ratom = 1ngliges. (3.37) = (3.33) themovement remplace par la masse H16 O1H] + 2[ 1H17 O1H] + 2[ 1H18 O1H] + [ 1H16 O1H] + ........ m A + rduite: mB of gas Athrough gas B, however, comme labondance2[de lisotope rare dun lment spcifique dans un type spcifi

16 1 17 1 16 2 m has to be replaced by thereduced mass: 2 (3.37) [ 2H O telles H] +que [2 H O H] +2H [ 218 H18 O1H] + 2[ 2 H H] + ........ 1 du 2O 18 divise par labondance de lisotope abondant. notre exemple deutrium d Les abondances de second ordre, par exempleDans 2 O en nominateur et H H O en R = atom 1 16 1 1 17 1 1 18 1 1 16 1 mA m B dnominateur, ont t ngliges. Dans ce contexte, le rapport isotopique molculaire (R ) est dfini A B 2[ H O H] + 2[ H O H] + 2[ H O H] + [ H O H] + ...... mol deau: = sur la thorie cintique des gaz). (3.33) Thesecond-order abundances, such as for in(3.33) (voir le document comme labondance de 2lisotope rare dun lment spcifique dans un 2 18 18 mA O in thenominator and 1Htype H spcifique O in de molcule stance H2 A + mB B 2lisotope 16 1 abondant. Dans notre exemple du deutrium dans la molcule divise par labondance de 2 [ H O H] 2 thedenominator, have been In this conH218O en nominateu Lesdeau: abondances de que second tellesneglected. que par exemple Les quations ci-dessus sont valables pour les isotopes abondants aussi pour ordre, les isotopes Rbien mol = 1 16 1 (see textbooks on thekinetic theory of gases). 2 [ H O H] ) is defined text molecular isotope ratio (Rle mol dnominateur, ontthe t ngliges. Dans ce contexte, rapport isotopique molculaire (voir document sur la thorie cintique des gaz). par le rapport rares.le Le fractionnement rsultant est alors donn des coefficients de pour les 16 diffusion [ 2H O1H] 2 as theabundance of therare isotope of aspecific R = Theabove equations hold for theabundant as well mol 1 16lisotope 1 comme labondance de rare dun lment spcifique dans un (3.38) type spcifi deux espces isotopiques. De plus, les masses molculaires peuvent tre remplaces par les se poids 2 [ cette H O H] La valeur raliste de dfinition rfre, par exemple, laby mesure des rapport element in aspecific type of molecule divided as for therare isotope. Theresulting fractionation Les quations ci-dessus sont valables pour les isotopes abondants aussi bien que pour les isotopes divise par labondance de lisotope abondant. Dans notre exemple du deutrium d molculaires M en numrateur et dnominateur: La valeur raliste de cette dfinition setheabundant rfre, par exemple, la mesure des rapports par spectromtrie laser (voir Sect.10.2.1.2), ou labsorption lumineuse permets la comp theabundance of isotope. In our ex-isotopiques is then given by theratio thediffusion coefrares. Le fractionnement rsultant est alors of donn par le rapport des coefficients de diffusion pour les deau: spectromtrie laser (voir Sect.10.2.1.2), ou labsorption lumineuse permets la comparaison de deux ample of deuterium inisotope, water: contrairement la spectromtrie de mas molcules, diffrant seulement dun for thetwo isotopic species. Furthermore, molcules, seulement dunpar isotope, la spectromtrie de masse (Kerstel et al., deux espcesficient isotopiques. De plus, les masses molculaires peuvent diffrant tre remplaces lescontrairement poids * M + M M M * D 2 16 1 A B A B 1999 ; comm. pers.). 1999 ; comm.2pers.). themolecular masses can be replaced by themo[ H O H] = = (3.34) molculaires M en D numrateur dnominateur: (3.38) *in Met MA M B denominator:Lquation 3.37R mol = 1 16telle AM B lar weights M numerator and tre r[-crite que: 2 H O1H] Lquation 3.37peut peut tre r -crite telle que:

1 17 1 2 [ 1H16 O17 H] 18 [ 1H [ 1H18 O1H] [ 1H16 O 2 H] 2 O H] 1 + R + R + R + ....... 1 + + + ..... 2 2 16 1 18 Le de dans fractionnement en C poursappauvrie la diffusion donc du CO lair 1 16 1 2 dans 18O (en Ratom les Rmol = Rmol Parfacteur diffusion lair, la vapeur deau en accord avec lois donnes H [ 1H O H] 2[ 1H16 O1H] 17 18 [la 2 O H] 1 + R + R + R + ....... 18 18

*D +M MB 2 17 16 par 1 1 exemple, 18 1 la 16 rapport 1 + 2 of + 2definition + 22refers, ....... B The realistic value for A de B MA A B 1this 16 1 valeur de raliste de[ 2cette dfinition se mesure Dans lexemple vapeur deau dans lair, La le(3.34) facteur fractionnement rsultant pour [rfre, H H 2[ 2 Hdes O 2 H] = *M A =de la diffusion H 16 O1H] [ (3.34) H16 O H] [ HO OH] H] [ [ H OO H] H] 2 Ratom = 1 to (3.39) 1 + + + .... * D * M M M M instance, themeasurement of isotope ratios 16 1 1 17 1 1 18 1 1 16 2 16 1 [ H O H]ou 1 H] [ 2 16 H] 2 16 1 A B A B spectromtrie (voir Sect.10.2.1.2), labsorption lumineuse permets la comp loxygne est (MB de lair est considr comme gal 20): 2 [ H H] [ 16 HOO O A B A B A = 18, MA =laser 29, M [ 2O H O H] [ 2+ H H] + [ H H O1H] 2 1+ ....... [ H O H] 1 16 (see 1 1 16 1 1 16 1where by laser spectrometry Sect.10.2.1.2), R = O H] 1 [ 17 H O H] 2[ 1H 18 O H] atom seulement 1 [ H isotope, 1 spectromtrie molcules, diffrant dun O la de mas 2 [ 1H16 O H]is compared [ H contrairement O1H] [ H isotopic H] [ 1H16 O 2 H] In theexample of water thelight absorption of+two 1vapour 1 + + En ..... Dans lexemple de la diffusion de vapeur deau diffusing dans lair, through le facteur de fractionnement rsultant pour Le ;premier facteur droite dans lquation Eq.3.391 est16 le rapport isotopique 1 1 16 molculaire. 1 1 bonne 16 1 1999 comm. pers.). [ H O H] [ H O H] 2[ H O H] 29 2 20 + 29 18 air, theresulting fractionation factor for oxygen is molecules, only differing in one isotope, contrary * 18 * approximation, les rapports isotopiques (3.35) molculaires dans le second facteur peuvent tre remplacs loxygne est (M lair est considr comme gal 29, MA = 18, MA = 20): =de B = 0.969 A A * (MBB of air is taken to be to isotopiques mass spectrometry [25] (priv.comm.). Lquation 3.37 peut tre r -crite telle que: 29 18 + 29 par les rapports atomiques: 20 29, MA=18, MA=20): Le premier facteur droite dans lquation Eq.3.39 est le rapport isotopique molc 17 18 2 1 1 1 + R + R + R + ....... 2 17 1 2 18 1 2 16 2 2 2 approximation, les le H] second Ratom rapports Rmol 17 isotopiques = 2R (3.40) [ molculaires H O [dans H O 2[facteur H O peuven H] 18 mol H] 29 18 deau 29 2 18 2 sappauvrie donc en 20 + 18 Par diffusion18 dans lair, la vapeur O (en accord avec les la 1 +lois R +donnes R(3.35) + 2R 1+ +....... + 2 16 1 + 2 16 1 .... = = 0 . 969 2 16 1 2 16 1 30 par les rapports isotopiques atomiques: [ H O H] [ H O H] [ H O H] [ H O H] 18 2 + 20 29 18 29 fin de la Part.3.4) de 31 : = 31 . Ratom = 44
[ 2 H17 O1H] [ 2 H18 O1H] 2[ 2 H16 O 2 H]
13
2 est:

*M + M

M M

fin de la Part.3.4) de 31 : = 31 .

deau:

mol 1 important 2 2 2 [ 1que H16 Ocelui H] considr pour les isotopes les moins lourds: 14 13 17 = rapports et 18 = par La valeur raliste de cette dfinition se rfre, par exemple, la mesure des isotopiques La valeur raliste de cette dfinition se rfre, par exemple, la mesure des rapports isotopiques par 2 2 fractionation of stable isotopes 14Sect.10.2.1.2), 18 abundance and spectromtrie laser (voir ou labsorption lumineuse permets spectromtrie laser (voir Sect.10.2.1.2), lumineuse permets la comparaison de deux la comparaison de deux (3.41) = 13ou labsorption et = 17 que molcules, diffrant seulement dun isotope, contrairement la spectromtrietandis de masse (Kerstel et al., molcules, diffrant seulement dun isotope, contrairement la spectromtrie de masse (Kerstel et al., 1999 ; comm. pers.). 1999 ; comm. pers.). tandis que 2

[ 2 H16 O1H] important que celui considr pour les isotopes les moins lourds: R = (3.38) Gnralement, pour les isotopes les plus lourds est pris comme deux fois plus mol 2 16 11 le 16 fractionnement 1 [ H OH H] O H] 2 [ 2 R = (3.38)
2

( )

( )
2

( )

( )

Eq.3.37 can be rewritten Lquation 3.37 peut tre r -crite telle que:
2

as:

14

17 1 que: Lquation 3.37 peut tre r -crite [ 2 Htelle O H] [ 2 H18 O1H] 2

14 18 (3.42) 2 and 18 2 17 (3.42) ratio. 2 13 2 17 approximalecular isotope Toet avery good 17 18 2 Lapproximation qui postule que ces fractionnements diffrent dun facteur 2 tire s 1 + R + R + R + ....... 2 2 Le premier facteur Rmol droite dans lquation Eq.3.39 le rapport isotopique molculaire. En bonne Ratom = 2ratios R (3.40) tion themolecular isotope inest thesecond mol Theapproximation that these fractionations dif1 + 17 R + 18 R + 2 R + ....... relation entre les masses molculaires comme prsente dans les quations 3.21 e approximation, les rapports molculaires dans le second facteur peuvent tre remplacs factor may be isotopiques replaced by theatomic isotope ra-diffrent Lapproximation qui postule que ces fractionnements dun facteur 2 tire son origine de la fer by afactor m+2 of 2 originates from therelation est une fonction de type (M+2)/M, tandis que m+1 isotopes les plus lourds, tios: par 44 les rapports isotopiques atomiques: between themolecular masses as les presented in relation entre les masses molculaires comme prsente dans les quations 3.21 et 3.23. Pour similaire de type (M + 1)/M. m+2 m+1For theheaviest isotope m+2 Eqs. 3.21 and 3.23. +est est une fonction isotopes les plus1lourds, 2 une fonction de type (M+2)/M, tandis que + 17 R + 18 R R + ....... 2 m+1 2 2 is afunction of (M+2)/M, while isotopiques is asimilar Ratom = RAyant (3.40) discut les bases thoriques des effets dans les paragraphes p mol (M17 mol similaire de R type + 1)/M. 18 2 1 + R + R + R + ....... function of (M + 1)/M. pouvons faire une approximation de lexposant dans la relation gnrale : Ayant discut les bases thoriques des effets isotopiques dans les paragraphes prcdents, nous (3.40) Having discussed thetheoretical background of

16 1 1 1 1 16 2 (3.39) Le premierle facteur droite lquation le O rapport molculaire. bonne CO2 et leau, respectivement: 2 dans [ 1H O H] Eq.3.39 [ 1est H17 H] isotopique [ 1H18 O H] [En H O H] spectively: 14 2 13 .......et 1 + + + approximation, les rapports isotopiques molculaires tre remplacs 1 dans 16 le 1second facteur 1 16peuvent 1 1 16 1 [ H O H] [ H O H] 2[ H O H] Thefirst factor on theright in Eq.3.39 is themo 14 13 par les rapports isotopiques atomiques:

2[ H O H] 14 13 13 ....... 1 + 2 14 + 12+ 16 2 1H] =+ 1[+ 1H] = + (13 ) 2 1 + 2 13 [ 2 H 16 O1 H] = 1[+ H16 O H16 O [ H2 O1H] donc, nous (3.39) 2 17 1 2 18 2 16 pour Ratom = 1 16 1 [ H O H O1H] 2[avons H O 2 H]le prlvement du CO2 par les plantes ainsi que 2 [ H O H] [ 1H17 O1H] [ 1H18 O1H] H] [ 1[ H16 O 2 H] so that for theCO2 uptake by plants as well as 1 + + + ....... 1 + + + ....... le CO et leau, respectivement: 1 16 1 1 16 1 1 16 1 1 [ H O H] 2 [ H 2 O 16H] 1 2 16 O1H] H] [ 2 H 16 O H]le prlvement [ H16 O [H Hpar Oles H] [ 2H O1que H] pour lchange isotopique entre donc, nous avons pour du 2[ CO plantes ainsi
2

16

= 1 + 14 = (1 + 13 ) = 1 + 2 13 + (13 ) 2 1 + 2 13

pour lchange

Ratom =

theisotope exchange between CO2 and water, re(3.39)

18

2 17

44

pouvons faire une approximation de lexposant dans la relation gnrale : isotope effects m + 2 sections, we are m+2 This result means that to afirst-order approxima m+1 in thepreceding

ln A / B RA RA = ou able to = make an approximation of theexponent tion theatomic isotope ratio is equal to amolecum+2 m +1 RB R ln m+1 A / B 2 +2 B in thegeneral relation: lar isotope m ratio. it was shown m+1 R A A /one ln m+for R A Although B = = (3.43) m+2 m +1 valid 1 m+reasoning ouis equally specific molecule, RB the R ln B A/ B ou more m = 12 pour le carbone, ou 16 pour loxygne. Les fractionnements par diffusion for theother molecules in Eq.3.39. Also for or (3.43) 3.35 et 3.43 im complicated molecules thedemonstration of Pour la diffusion de vapeur deau dans lair, les quations calculables. ou m = 12 pour le carbone, ou 16 pour loxygne. Les fractionnements par diffusion sont facilement theproof is analogous.
calculables. Pour la diffusion de vapeur deau dans lair, les quations 3.35 et 3.43 impliquent

Theapproximations made are indicated as firstorder. However, if we use values theapproximation is even better, because almost equal approximations occur in theR values of thenominator as well as thedenominator of Eq.3.40 (cf. Sect.4.3.1). 3.7. Relation between fractionations for three isotopic molecules

where m=12 for carbon or 16 for oxygen. Thefractionations by diffusion are easily calcu45 lated. For thediffusion of water vapour through air Eqs.3.35 and 3.43 result in: ln 18 / ln 17 = 1.93 whereas according to Eqs.3.36 and 3.43 for thediffusion of CO2 through air: ln 14 / ln 13 = 1.96 In terms of fractionation this comes to:
18

For some isotope studies, it is of interest to know therelation between thefractionations for more than two isotopic molecules. For instance, water contains three different isotopic molecules as far as oxygen is concerned: H216O, H217O and H218O; carbon dioxide consists of 12CO2, 13CO2 as well 14CO2. Thequestion now is, whether there is atheoretical relation between the17O and 18O fractionation with respect to 16O (for instance, during evaporation) and between the13C and 14C fractionation with respect to 12C (for instance, during theuptake of CO2 by plants). Generally thefractionation for theheaviest isotope is taken twice as large as that for theless heavy isotope:
14

1.93 17and14 1.96 13

Calculating theexponent for fractionation effects in general is quite elaborate. Therelatively simple case for theCO O2 isotopic equilibrium may serve as an example [23]. Theisotope exchange reactions are:
18

O16O + 12C16O 16O2 + 12C18O

and
17

O16O + 12C16O 16O2 + 12C17O

=( )
13

and

18

=(
17

(3.41)

while

Inserting theproper mass numbers and thevibration frequencies: (12C16O)=6.501013/s and (16O16O)=4.741013/s in Eqs.3.18 and 3.29, thevalues at 20C are: 31

. . . .
and

17 18 O O et et 18 O O Dans Dans le le premier premier cas, cas, une une dtermination dtermination exprimentale exprimentale de de la la relation relation entre entre 17 Une Unesrie sriedchantillons dchantillonsdeau deaunaturelle naturelleaat tlectrolytiquement lectrolytiquementconvertie convertieen enoxygn oxygn

17 1 analys analyspar parspectromtrie spectromtriede demasse. masse.La Larelation relationrsultante rsultanteentre entreles lesvaleurs valeursde de17 et et18 INTRODUCTION (Meijer (Meijeret etLi, Li,1998) 1998)selon: selon:
18 18 17 17(1 (1 ,8935 ,8935 00 , 005 , 005 )) 1 1+ + = (1 (1 + +17 )) + 18 = = (1 + )(1.8935 0.005) (3.45)

. . . .

Malgr Malgr cela, cela, dans dans de de nombreux nombreux cas cas de de routine routine pour pour lesquels lesquels la la prcision prcision obtenue obtenu tainable precision is limited or irrelevant, we may irraliste, irraliste,nous nouspouvons pouvonsquand quandmme mmeutiliser utiliserla larelation relationsuivante: suivante:

Despite this, in many routine cases, where theob-

still use therelation:

et et and

so that:

++ 22 lnmm ln = =2 2 m m ++ 11 ln ln

m m ++ 22

m m ++ 11 = =(( ))

22

= 2m+1 (3.47) + + 11 = =2 2 mm at least with aprecision of 10%. In this respect, Applying theequations to poly-atomic molecules . avec, avec,au auminium, minium, une uneprcision prcisionde de 10%.Dans Dans cette cetteoptique, optique, nous continuerons continueronsdappli dappl we will continue to10%. apply thefactor of 2 innous therecan only result in approximate values. However, 13 13 12 12 14 14 12 12 13 12 14 12 dans dans les les relations relations entre entre les les rapports rapports isotopiques isotopiques C/ C C et et C/ C/ C C pour pour les les processus processus na n C/ C and C/ C isotope ralation between the calculations on theexchange equilibria such as tios for natural processes: CO CO2 et CO2 CH4 result in: (h=6.626 * 1034 Js; k=1.38 1023 J/K).
m+2 m m ++ 22
14 14 13 = =2213

. . .

(3.46)

ou: ou:

or:

= 2 13 (3.44) 14 comme commeoriginellement originellementutilise utilisepar parCraig Craig(1954). (1954).La Laprcision prcisionde delanalyse lanalysedu du14 C Cne ne 14 C as originally used by [28]. Theprecision of a pour pour permettre permettre une une vrification vrification exprimentale exprimentale de de la la relation relation de de lquation lquation 13 an experimen 14 analysis ismolcules not sufficient to allow C Cet etle le14 C. C. fractionnements fractionnements pour pourles les molcules contenant contenant le le13 tal verification of therelation of Eq.3.42 between In one case an experimental determination of Dun Dunautre autrect, ct,lquation lquation3.44 3.44doit doittre treapplique appliquesi siles lesfractionnements fractionnementsimpliqus impliqusso s therelation thefractionations for 13C and 14C containing mol. between 17O and 18O has been posles lesmesures mesuressuffisamment suffisammentprcises. prcises. sible. Aseries of natural water samples was elececules. trolytically converted into oxygen which was On theother hand, Eq.3.44 is to be applied if then analysed mass spectrometrically. Theresult17 18 thefractionations involved are large and themeaing relation between the and values was reported as [27]: surements sufficiently accurate.

. . . rather than in =2 [26].

14

32

ABUNDANCE VARIATIONS by NATURAL PROCESSEs

4 4

4. ABUNDANCE VARIATIONS by NATURAL PROCESSEs VARIATIONS DES ABONDANCES PAR Chapitre 4 LES PROCESSUS NATURELS

For the specific isotopes mentioned in Eq.4.1 In thepreceding chapter we have defined isotope Pour les isotopes spcifiques mentionns dans lquation 4.1, les valeurs respec therespective values are indicated by thesymChapitre 4 (abundance) ratios in various chemical comindiques par les symboles: bols: pounds. Furthermore, we have presented atheo1 12 retical treatment of thephysical phenomenon ( 2 H/ H) A respectives (13 C/sont C) (18 O/ 16 O) Pour les isotopes spcifiques mentionns dans lquation 4.1, les valeurs de 2 13 = 1 dans des = 13 12 A 1 18 = 18 16 A 1 of isotope fractionation. In dfini this chapter we will Dans le chapitre prcdent, nous avons les rapports (abondances) 2 isotopiques 1 ( H/ H) r ( C/ C) r ( O/ O) r indiques par les symboles: discuss trs thebackground of various processes occomposs chimiques varis. Nous avons ensuite prsent un traitement thorique du phnomne 2 12 18 16 curring in nature, that may cause variations in (isotopique. H/ 1H) (13 C/ nous C) Aallons (les O/ O) physique de fractionnement bases des sachant quediscuter les les plus souvent utiliss sont 2H ou D, 13C, et 18O, respec 2 13 chapitre, 18 symboles A nombreux A Dans ce = 1 = 1 = 1 (4.2b) (4.2b) 1 18 16 theisotope ratios. processus qui se produisent dans induire variations les rapports ( 2 H/ H) rla nature, pouvant (13 C/ 12 C) r des O/dans O) r Toutefois, dans ce ( volume, nous crirons les nombres de masse reprsentant lisotop isotopiques. Theequations that will be derived can be ex13 18 par un exposant avant le , O, comme pour le symbole R et le symbole Dans le sachant chapitre prcdent, nous dfini utiliss les rapports (abondances) isotopiques dans des themore often used symbols are 2H or isotopique lui-m que les symboles lesavons plus souvent sont 2H ou where D, C, et respectivement. pressed practically without approximation in iso13 18 Les quations qui en sont drives peuvent tre exprimes pratiquement, et sans aucune une simplification deC, ces symboles et librant de lespace pour dautres exposants ou i and respectively. D, thorique composs chimiques trs varis. Nous avons ensuite prsent un traitement du O, phnomne tope ratios R volume, values) as well as in les amore or less Toutefois, dans ( ce nous crirons nombres de masse reprsentant lisotope rare concern approximation, en rapports isotopiques (valeurs R) aussi bien que, sous une forme plus approximative, physique de fractionnement isotopique. Dans ce chapitre, nous allons discuter les bases desvolume nombreux However, this wepetites, will write approximated format in values. Comme valeurs de in dans la nature sont elles themass sont gnralement donnes3 parun exposant avant le , comme pour le symbole R et leles symbole isotopique lui-mme, faisant ainsi en notation . se processus qui produisent dans la nature, pouvant induire des number variations dans les rapports isotope concerned indicating therare by 3 dfiniespour en (pour mille ou parties par millier 10 ). Nous devons insister sur l une simplification de ces symboles et librant de lespace dautres exposants indices. isotopiques. asuperscript before the , as with the R symnest pas une unit, mme si cest ce qui est quivalent bols un facteur 103 et que ce 4.1. les Use ofde values and isotope and theisotope symbol itself, 4.1 UTILISATION DES VALEURS sont ET DES REFERENCES ISOTOPIQUES Comme valeurs dans la nature petites, elles sont gnralement donnes3 bien que non thus making Les quations qui en sont drives peuvent tre exprimes pratiquement, et sans aucune un nombre et sans dimension. De faon sim suggr. Unethesymbols valeur est simplement references simpler and leavingpetit space for other Nous devons insister sur le fait que dfinies en (pour parties R) par millier que, 103). 3 est approximation, en rapports isotopiques (valeurs aussi bien sous une forme plus approximative, Les rapports isotopiques tels que mille superand subscripts. dans la Part.3.3, il est incorrect dutiliser /10 la place de dans les quations ma 3 Isotope such10 as et que ce nest pas une unit, mme si cest ce qui est le plus souvent quivalent ratios un facteur en notation . faon viter doublier que est un nombre, il est possible de choisir dcrire da As thevalues of inpetit nature are small, they are 2 13 simplement un 18nombre petit et sans dimension. est De faon similaire dfini suggr. Une valeur 3 H C O 2 13 18 (en )10 la -although place , peu pratique mathmatiques: generally given not definedin tel quil est. (4.1) R= 1 R = 12 R = 16 (4.1) dun simple 3 /10 REFERENCES la place de dans les quations mathmatiques. De 3 dans la Part.3.3, incorrect dutiliser H il est C O 4.1 UTILISATION DES VALEURS ET ISOTOPIQUES DES (per mill parts per thousand 10 ). We have indiquent des abondances plus faibles en isotope rare dans valeurs de faon viter doublier que est un petit nombre,Les il est possible dengatives choisir dcrire quations to to emphasise that dans isles equivalent thefactor are generally as absolute numbers. Les rapports isotopiques tels not que reported 3 positives des que le matriel de rfrence, etsont des valeurs desuggested. (en )103comme la place dun simple , dans peu pratique tel and quil est. mathmatiques: ne sont gnralement pasconsidrs des nombres absolus. Les principales raisons en les is not aunit as is often Ateneurs plus importa 10 Themain reasons are: value is merely asmall, dimensionless number. suivantes: 2 de ngatives 13 indiquent des 18 abondances (Eq.3.5) et , la seule diffrence est que, tandis q En comparant de plus faiblesles en dfinitions isotope rare dans les chantillons Les (1) valeurs H C spectrometers, O suitable 2 13of mass 18 thetype for Similarly to defined R = 1 de masse, R = 12 utilisables R =pour (4.1) in Sect.3.3, it is incor16 1) les spectromtres mesurer les abondances isotopiques avec une le rapport isotopique dun 3 compos (ici B) relativement un autre compos (A positives des teneurs plus importantes. que dans measuring le H matriel deisotope rfrence, et des valeurs decomme C O with abundances high instead of in mathematical rect to use /10 sensibilit suffisamment importante pour pouvoir dtecter des variations naturelles trs faibles, tant que rapport isotopique dun compos (maintenant A) relativement un matr equations. In order to ne avoid thenegligence sensitivity in order to detect very small En comparant les dfinitions de (Eq.3.5) et , la seule diffrence est que, tandis que a t dfini permettent absolument pas dobtenir des rapports isotopiques fiables (voir Part.11.2); standard (r). principales to realise that en issont asmall natural variations, are basically not absolus. suitable ne sont gnralement pas considrs comme des nombres Les raisons les number, one may est dfini en equations: comme le rapport isotopique dun compos (ici B) relativement un autreto compos (A), choose write in mathematical for obtaining reliable absolute ratios (see suivantes: 2) la ncessit comparaisons internationales implique lutilisation de auxquelles lesrfrence Bien que dans les rfrences quations tires de cede chapitre, le format , puisse tre appliqu p 3 tant que de rapport isotopique dun compos (maintenant A) relativement un matriel instead of merely , impractical (in )10 Sect.11.2); chantillons doivent tre rapports; les les processus naturels avec une prcision accessible par linstrumentation analytiq 1) les spectromtres abondances isotopiques avec une standard (r). de masse, utilisables pour mesurer though it is. (2) thenecessity of pour international comparicapacit de calcul des petits calculateurs de poche utiliss sur le terrain a gn sensibilit suffisamment importante pouvoir dtecter des variations naturelles trs faibles, ne 3) lutilisation des rapports isotopiques conduirait reporter des rsultats avec un grand nombre de Bien que son dansrequires les quations tires dereferences ce chapitre,to le which format , puisse tre appliqu indicate pratiquement tous Negative values lower abundances theuse of superflue les approximations. les laboratoires isot permettent absolument dobtenir des rapports isotopiques fiables (voir Part.11.2); Les valeurs de dtermines par of chiffres aprs la virgulepas (5 ou 6); les processus naturels avec une prcision accessible par linstrumentation analytique moderne,than la in therefertherare isotope in these samples thesamples have to be related; alors tre transformes en valeurs R en appliquant (rcriture de lquation 4.2): 2) de internationales de rfrences auxquelles les ence material, positive values point to higher capacit absolus de comparaisons calcul des calculateurs de poche utiliss sur le terrain a gnralement rendue 4) la lesncessit rapports sont, enpetits principe, moins implique utiles (et lutilisation moins utiliss) que les variations de ces (3) theuse of isotope ratios would lead to reportabundances. R = Rr(1 + ) chantillons doivent tre rapports; mme rapports pendant les transitions phases oudtermines entre molcules. superflue les approximations. Lesentre valeurs de ing results as numbers consisting of alarge par les laboratoires isotopiques peuvent alors tre transformes R en appliquant (rcriture de lquation 4.2): Comparing the definitions (Eq.3.5) and , sont les rapports isotopiques matriaux derfrence internatio ou les valeurs R 3) lutilisation des rapports conduirait reporter des rsultats un grand nombre de of des r avec number (5 isotopiques oren 6)valeurs of Ainsi, une abondance isotopique estdigits; gnralement reporte comme une dviation du rapport theonly difference is that, whereas was defined dfinis plus loin dans le Chapitre 7. En se rfrant la relation entre le rapport chiffres aprs la virgule (5 ou 6); isotopique dun Une relativeless par relevant rapport un chantillon de rfrence ou R = Rr(1 + ) dfinition (4.3) (4) chantillon. absolute ratios are in principle as theisotope ratio of acompound (then B) relconcentration isotopique (Part. 3.1), cette concentration isotopique, C, peut standard, r: 4) les rapports absolus moins utiles des (et during moins utiliss) que les variations de ces than thechanges in ratios occurring ative to another compound (A), is defined as sont en lesprincipe, rapports isotopiques matriaux de rfrence internationaux qui seront ou les valeurs Rrsont, transforme en par insertion de lquation 3.3b: transitions between phases or molecules. mme rapports pendant les transitions entre phases ou entre molcules. theisotope ratio of acompound (now dfinis plus loin dans le Chapitre 7. En se rfrant la relation entre le rapport isotopique et la A) relative R 3 to thestandardised reference material R dviation C 1 ( 10 (4.2a) A/r = A concentration isotopique (Part. 3.1), cetteis concentration isotopique, C,1 peut maintenant tre (r). Therefore, an isotope abundance generally Ainsi, une abondance isotopique est) gnralement reporte comme une du rapport = 1 = 1 Rr Rr C Although in R theequations reported adeviation theisotope of un transforme enas par insertion deof lquation 3.3b: r 1 isotopique dun chantillon. Une dfinition relative par ratio rapport chantillon de rfrence ou to be derived in this chapter the format can be applied to practically 13 asample A relative to that of areference sample standard, r: Exemples: le carbone naturel contient environ 1%attainable datomes by de C; le carbone, R 1 C 49 all natural processes to theprecision or standard, 1 (4.4) = r: 1 = 13 atomes a donc une valeur ( concentration leve, et bien sur absurde, en C de 99% thecalcuRr Rr 1 C themodern analytical instrumentation, RA 3 3 (4.2a) A/r = 1 ( 10 ) capacity of (4.2a) small pocket calculators used = 0,0112372,lation Sect.13 7.1.3) de 8809 10 . le generally carbone, en prenant Exemples: R le environ 1% datomes r carbone naturel contient in de the C; field has come une to make the ap-

VARIATIONS DES ABONDANCES PAR LES PROCESSUS NATURELS

concentration leve, et bien sur absurde, en 13C de 99% atomes a donc une valeur (vs PDB-CO2: Rr 49 = 0,0112372, Sect. 7.1.3) de 8809 103. 50

33

50

que dans le matriel de rfrence, et des valeurs de positives des teneurs plus importantes.

. Les valeurs de R et sont tandis que les de faon similaire lquation pour et , la 3.6 seule diffrence est que, tandis que amultiplicatives, t dfini En comparant les dfinitions de (Eq.3.5) et peuvent seulement et approximativement En valeurs de en dautres termes, le comme le rapport isotopique dun compos (ici B) relativement un autre compos sadditionner. (A), est dfini , tel que dfini par 3.5, est matriel presque de quivalent fractionnement INTRODUCTION tant que rapport isotopique dun compos (maintenant A) lquation relativement un rfrence la diffrence de composition isotopique entre deux phases: standard (r).
Bien que dans les quations tires de ce chapitre, format ,R puisse tre appliqu proximations superfluous. The le R values deliv1 + B / r pratiquement tous B B / Rr = = = = 1 B / r A/ r 1 1 1 / / B A B A ered by isotope laboratories can easily belinstrumentation transles processus naturels avec une prcision accessible analytique moderne, la 1+ R A par R A/ r A / Rr formed into R values by applying (rewritten from capacit de calcul des petits calculateurs de poche utiliss sur le terrain a gnralement rendue (4.8)

(4.8)

For thereaction A B, B/Ais thechange in isosuperflue lesEq.4.2): approximations. Les valeurs dtermines les laboratoires isotopiques peuvent B/Acorrespond aupar changement de composition isotopique (gal au "nouveau" Pour la raction AB, de topic composition (equal thenew minus alors tre transformes en valeurs R en appliquant (rcriture de lquation 4.2): moins l "ancien" ; cf. Part. 3.3).
R = Rr(1 + fait ) Rque (4.3) Du des conventions strictes gouvernent lutilisation rfrences, nous allons gnralement where the Becausedes strict conventions govern theuse of r values are theisotope ratios of theinternational reference materials to be desupprimer lindice r et dsigner lchantillon par un indice ou (A) la place de et (A). references, we will generally A internationaux qui seront A / rdropr thesubscript ou les valeurs Rr sont les rapports isotopiques des matriaux de rfrence fined later in Chapter 7. Referring to therelation r and designate thesample dfinis plus loin dans le Chapitre 7. En se rfrant lade relation entre le rapport isotopique et la by asubscript A or et est couramment approche par: La possibilit dadditionner les valeurs between isotope ratio and isotope concentration (A) instead of and r(A). A / r concentration isotopique (Part. 3.1), cette concentration isotopique, C, peut maintenant tre transforme en par insertion into delquation 3.3b: Eq.3.3b: B/A B A+ betransformed by inserting

R = Rr(1 + ) (4.3)

theold (cf. Sect.3.3).

(Sect.3.1), theisotope concentration, C, can now

=

R 1 C Ceci signifie que, valeur en 13 de 8 est assimil 1 = si 1 un CO2 de lair avec une (4.4) par les plantes avec un (4.4) (4.9) B A + Rr Rr 1 C du carbone organique sera de 25. fractionnement isotopique en carbone de 17, la valeur de 13 B/A 13 This means that if air-CO Examples: natural carbon contains about 1 atom le carbone, en prenant une2 with a value of Exemples: le carbone naturel contient environ 1% datomes de 13C; Variations dabondances isotopiques 13 8 is assimilated by plants with acarbon iso13 Variations dabondances isotopiques % of 13C; carbon an en absurdly highatomes C conVariations dabondances isotopiques C de 99% a donc une valeur (vs PDB-CO concentration leve, et bien sur with absurde, 2 : Rr tope fractionation of 17, the13 value of centration of 99 atom % thus has a value (vs Variations = 0,0112372, Sect. 7.1.3) de 8809 103. dabondances isotopiques theplant carbon is 25. Si les valeursPDB-CO doivent par rapport une rfrence r', plutt que par rapport 51 : tre Rrdonnes =0.0112372, Sect.7.1.3) of secondaire, Variations dabondances isotopiques Si doivent2tre tre donnes par rapport rapport une une rfrence rfrence secondaire, r' r', , plutt plutt que que par par rapport rapport Si les les valeurs valeurs8809 doivent donnes par secondaire, 3 10 . la rfrence primaire r, une quation de conversion est alors ncessaire. la primaire r est alors Si rfrence les valeurs doivent tre quation donnes de parconversion rapport une secondaire, r', plutt que par rapport la rfrence primaire r, , une une quation de conversion est rfrence alors ncessaire. ncessaire. Chapitre 4 4.2. concentration, If values are to be given relative to asecondary 50 Si les valeurs doivent tre quation donnes de parconversion rapport une rfrence secondaire, r',Tracer plutt que par rapport la rfrence primaire r , une est alors ncessaire. A partir des rapports isotopiques: A partir des rapports isotopiques: A partir des rapports isotopiques: reference, r', rather than to theprimary reference amount of tracer la rfrence primaire r, une quation de conversion est alors ncessaire. A partir des rapports isotopiques: r, aconversion equation is needed. 4.2 CONCENTRATION ET TAUX Natural isotopes can be used DE as TRACEUR tracers to folRA R /R R R /R Chapitre 4 A A r R R /R A partir des rapports isotopiques: A r A A r (4.5) =theisotope ratios: (4.5) = low elements of thewater cycle in their natural From (4.5) = Les isotopes naturels peuvent tre utiliss comme traceurs pour suivre les lment R R /R R /R Rr' R 2 r' A Ar' r r' r r' r' r H and course. For instance, theabundance of (4.5) = leau au cours de leur trajet naturel. Par exemple, labondance de 2H et 18O dans les pr Rr' RCONCENTRATION 18 R /R A A /R r 4.2 R ET TAUX DE TRACEUR r' r O in precipitation can be applied to unravelling = (4.5) tre(4.5) applique pour sparer les diffrents composants de lhydrogramme de crue. C ou Rr' Rr' /Rr ou thevarious components of therunoff hydrograph. ou Les isotopes naturels peuvent tre utiliss comme traceurs pour suivre les lments constitutifs deles diffrents compartiments du bi permet alors de calculer la quantit de traceur dans ou This application comes to calculating theamount 2 18 or leau au cours de leur trajet naturel. Par exemple, labondance de rgional. H et O dans les prcipitations peut A 1 + bien local que 1 + ou of tracer in thedifferent compartments of thelo/ r A / r A / r les diffrents composants de lhydrogramme de crue. Cette application 1 + sparer A // r 1 + = pour 1 + r '' = tre 1 applique + A = cal or regional water budget. 1 + ' r A''/ Dans la Part.3.1, nous avons dfini, par exemple, la concentration isotopique de l18 r /r r 1 +alors = calculer AA/ /r r 1 + ' de permet r '/la r quantit de traceur dans les diffrents compartiments du bilan en eau, aussi 1 + 1+ r A'/ /r r In Sect.3.1 we have defined theisotope concenque: 1 + Aque / r' = bien local rgional. Et donc, 1 + Et donc, r '/ r tration of, for instance, 18O in water as: Et donc, Et donc, Dans 18 18 leau tel 18 follows la Part.3.1, nous avons dfini, par exemple, la concentration isotopique de l18 OH dans quantit de H2 O R (H 2 O) 18 2 O A [H O] = = = 18 Et donc, que: / r r ' / r A/ r r '/ r 2 16 18 18 (4.6) = (4.6) = A / r ' quantit d'eau 1 + R (H O) H 2 O+ H 2 O A/ r' 2 r '/ r 1 / r + r AA /+ r/ r r ''/ r '/ r (4.6) = 1 (4.6) A (4.6) A//rr' ' = A1 r '/ r 18 18 18 /+ r+ r '/ r '/ r quantit A/ r' = 1 (4.6) de H 2 O H2 O R (H 2 O) 18 18 = = [H O] = composs R (H 2 O) (4.10) et dans la notation : entre (4.10) Cette quation est galement utile pour faire la conversion entre deux phases ou 1+ 2 r '/ r Cette quation est galement utile pour faire la conversion16 entre deux ou entre deux deux composs 18 phases 18 quantit d'eau 1 + R (H O) H 2 O+ beH2 O This equation is also useful for converting 2 A Cette quation est utile pour faire la conversion entre entre deux phases ou entre deux composs A et et B: B: Cette quation est galement galement utile pour faire la conversion deux phases ou entre deux composs tween two phases or compounds Aand B: 18 18 18 18 18 18 O ] = R { R ( H [ H Cette quation est galement utile pour faire la conversion entre deux phases ou entre deux composs 2 in r 2O) / Rr} = Rr {1 + } A et B: and the notation: A et B: et dans la notation B/A : A et B: = B/A A/B (4.7) B/A (4.7) 18 18 (4.7) 18 A/B = B/A [H218O] = R R(H / 18 Rpeut, Rr {1 + 18de } traceur. Ceci appar Maintenant, lisotope rare en que tel ne servir 1 + B/A r {tant 2O) r} = seul, 1 + B/A B/A A/B = [H (4.7) 18 18 18 18 18 18 B/A B/A (4.11) O ] = R { R ( H O ) / R } = R {1 + } (4.11) 2 B/A r 2 r r nous analysons le cas dun hydrogramme de crue. Si, pendant un pisode pluvieux, l + A/B = =1 (4.7) B/A B/A (4.7) similar to theEq.3.6 A/B B/A for . Values of R and are 18 1 + B/A + B/A . Les valeurs de R et multiplicatives, tandis que les de 3.6 gale celle du flux de base (= eaux souterraines se avec therare une valeur .and Les valeurs deare R produisent et sont sont Now multiplicatives, tandis que les de faon faon similaire similaire 1lquation lquation 3.6 pour pour isotope as such can not simply serve multiplicative, whereas values only Maintenant, lisotope rare en tant que tel ne peut, seul, servir de traceur. Ceci tandis apparat clairement si changement dans le ruissellement, et donc nous ne sommes pas et peuvent seulement et approximativement sadditionner. En dautres termes, le valeurs de . Les valeurs de R et sont multiplicatives, que les de faon similaire lquation 3.6 pour as thetracer. Thistermes, becomes et peuvent seulement et approximativement sadditionner. En dautres le clear if we consider en mesure de rec valeurs de approximately additive. In other words, thefracnous analysons le cas dun hydrogramme de crue. Si, pendant un pisode pluvieux, les prcipitations . Les valeurs R sont et sont multiplicatives, tandis de faon similaire lquation 3.6 pour . approximativement Les valeurs de Rde etsadditionner. multiplicatives, que les de faonde similaire lquation 3.6 pour apporte par les prcipitations dans le ruissellement total. Les thecase therunoff hydrograph analysis. Ifpluies dur- ne peuvent tre , tel que par lquation 3.5, est presque quivalent la diffrence de fractionnement tionation et peuvent seulement et Enof dautres termes, le que les valeurs , as dfini defined by Eq.3.5, is almost equal , tel que dfini par lquation 3.5, est presque quivalent la tandis diffrence de fractionnement 18 18 gale celle du flux de base (= eaux souterraines), il ny a aucun se produisent avec une valeur ing astorm rain would fall with a value equal il est possible de les distinguer isotopiquement du flux de base. Ainsi, la concentration et peuvent seulement approximativement sadditionner. En dautres termes, de le valeurs de de isotopique to thedifference in isotopic composition between composition entre deux phases: et peuvent seulement et approximativement sadditionner. En dautres termes, le valeurs , tel que par et lquation 3.5, est presque quivalent la diffrence fractionnement composition isotopique entredfini deux phases: to that of the base flow (=groundwater), there changement dans le ruissellement, et donc nous ne sommes pas en mesure de reconnatre la part two tre dfinie comme la dviation la concentration en isotope rare partir dun nivea par lquation 3.5, 3.5, est presque quivalent la diffrence de fractionnement composition isotopique entre deux phases: ,phases: , tel tel que quedfini dfini par lquation est presque quivalent dela diffrence de fractionnement would be no isotopic change in therunoff and so 18 apporte par les prcipitations dans le ruissellement total. Les pluies ne peuvent tre traces que si 1 + / R R R dans notre cas, la teneur en du flux de base (= moyenne des eaux s RB RB composition isotopique isotopique entre deux B B/ /r r est, B phases: B / Rr r 1 = 1 + qui B = 1 = 1 = 1 (4.8) composition entre deux phases: not be able to recognise 1distinguer = 1 = 1 = du flux 1base. B (4.8) B / r A r B/ /we r would A/ /la r concentration /A /A B/ A = B A les il est possible de isotopiquement de Ainsi, en traceur doit theprecipita/ Rr 1 R RA concentration du traceur est alors dfinie comme: 1+ + RB A A B A / Rr A/ /r r 1 tion A 1 = RB in therunoff. Theprecipitation can only be = 1 = 1 = (4.8) B/ A B/ A /r /r tre dfinie comme la dviation de la concentration en isotopeBrare A partir dun niveau de base donn, 1 B / RA R /R 1+ + RB R r r AR r/ A/ / r B / A = B / A 1 = RB 1 = 1 = 1 (4.8) 1 + R R / r 18 A / r B / r (= 18 eaux souterraines). qui est, dans cas, laBteneur enB 18 rdu flux de base moyenne des + RA [ H correspond de composition isotopique (gal au Pour Obase = 18Rr {18(4.8) 18La B /A = B, notre 1= au 1R =changement 1 1 = B1 [H 2 O 2 base} /B/A correspond au changement de composition isotopique (gal au ]"nouveau" "nouveau" Pour la la raction raction A B, A / Rr A/ r A B A B /]r A/ r B/A / 1 + R R R A A r A / r concentration du traceur est alors dfinie comme: 34 A ; Part. 3.3). l B/A correspond au changement de composition isotopique (gal au "nouveau" Pour la raction B, ; cf. cf. Part. 3.3). moins moins l "ancien" "ancien" que valeur 18R de la rfrence internationale (i.e. no nous avons insr 18R correspond au changement de Ici composition isotopique (gal au "nouveau" Pour la raction A B, r en tant B/A ; cf.18 Part. 3.3). gouvernent moins l "ancien" Du fait que des conventions strictes lutilisation des rfrences, nous allons gnralement 18 18 18 18 Du fait que des conventions gouvernent lutilisation de descomposition rfrences, nous allons gnralement H O ] strictes [H2 O } (4.12) correspond au R changement isotopique (gal Pour la raction A 2 base] = r { base qui sera introduite dans le chapitre 7). au "nouveau" B/A ;[B, cf. Part. 3.3). moins l "ancien" supprimer lindice r lchantillon par indice ou (A) la place de et (A). Du fait que des conventions strictes gouvernent lutilisation des rfrences, nous allons gnralement A / r r supprimer lindice r et et dsigner dsigner lchantillon par un un indice A ou (A) la place de et (A). A A/r r moins l "ancien" ; cf. Part. 3.3). Si la comparaison entre le taux de ruissellement et la hauteur de prcipitations, com

Theadditivity of and values is commonly ap(4.9) proximated by:

[H 2 O] =
et dans la notation :

18

quantit de H 2 O H O R (H 2 O) = 16 2 = 18 18 quantit d'eau H 2 O+ H 2 O 1 + R (H 2 O)

18

R (H 2 O) (4.10)

ABUNDANCE VARIATIONS by NATURAL PROCESSEs

[H218O] = 18Rr {18R(H2O) / 18Rr} = 18Rr {1 + 18}

18 isotope from acertain base gale celle du flux de base (= eaux souterraines), il ny a aucun se produisenttherare avec une valeur concentration 4.3.1. Mixing of reservoirs of 18 value ofne the base flow level,lein our case the changement dans ruissellement, et donc nous sommes pas en mesure dethesame reconnatre la part compound (=average groundwater). Theconcentration of apporte par les prcipitations dans le ruissellement total. Les pluies ne peuvent tre traces que si two (or more) quantities of acertain compound thetracer is thenisotopiquement defined as: du flux de base. Ainsi, laIf il est possible de les distinguer concentration en traceur doit with different values are being mixed (for intre dfinie comme la dviation de la concentration en isotope rare partir dun niveau de base donn, Fig.4.1 Reprsentation schmatique de two (A):different le mlange de deux quantits dun origins, stance, theCO Rr {18 18base} (4.12) [H218O] [H218Obase] = 1818 2 in theair of qui est, dans notre cas, la teneur en du flux de base (= moyenne des eaux souterraines). La suchdeux as marine and biospheric), the value of le mlange et la avec compositions isotopiques diffrentes, et (B): concentrationHere du traceur est alors dfinie 18 comme: Rr as the18R value of composs we have inserted themixture can be ou calculated from amass baldiffrents deux phases du mme compos avec de theinternational reference (i.e. standard, to be in- isotopiques ance equation (Fig.4.1A). diffrentes qui seront sujet des changes isotopiques et 18 18 [ H218O] [in H2Chapter Obase] = 7). Rr {18 18base} (4.12) troduced dernier ressort un de fractionnement (). offacteur acertain compound with an isoN1molecules

with different Maintenant, lisotope rare en tant que tel ne peut, seul, servir conde traceur. Ceci apparat clairement si isotopic from the base flow. Therefore, the tracer composition centration has to be defined as the of nous analysons le cas dun hydrogramme de crue. Si,deviation pendant un pisode pluvieux, les prcipitations

traced if it can be distinguished isotopically

4.3. Mixing of reservoirs

(4.11)

RN R N RN where W denotes theamount of water. = 1 1 + 2 2 or RN R1 N1 + R2 N 2 Comparing specifically the amount of runoff Q 1 + R 1 + R1 1 + R2 ou W correspond la quantit deau. En comparant spcifiquement la quantit de ruissellement Q et la and theamount of precipitation, P now comes to (4.15) hauteur de prcipitations, P permet alors de calculer le rapport: avec N = N1 + N2. Lapproximation est valable pour R R1 R2 (notons que les vale calculating theratio: N2. Theapproximation is valid N=N ngliges parwhere comparaison avec 1 + lunit). 18 for R R1 R2 (note that theR values have not ( Q Q )i En remplaant les valeurs de R par Rr (1 + ) et en indiquant les contributions fraction i been neglected in comparison to 1). (4.14) (4.14) 18 ( P P ) j par f1 (= N1/N) et f2 (= N2/N), ou f1 + f2 = 1, la valeur de du mlange est: Replacing theR values by Rr (1 + ) and denotj ing thefractional contributions to themixture by for anumber of time periods i and j, respectively f1 (= N1/N) and f2 (= N2/N), where 1 + f2 = 1, the (i may equal j, depending on thequestion). value of themixture is: 52

Ici nous avons insr 18Rr en tant que valeur 18R de la rfrence internationale (i.e. notion de standard, theabundant, R1N1/(1 + R1) molecules of therare case, theamount of runoff and theamount of prequi sera introduite dans le chapitre 7). isotopic species (cf. Eq. 3.3).If this quantity is N1 molcules dun compos donn avec un rapport isotopique R1 contiennent N1/(1 + cipitation, we have to introduce theamount of (with isotopic mixed with another quantity N lisotope abondant, et R N /(1 + R ) molcules de lespce isotopique rare (cf. E 2 Si la comparaison entre le taux de ruissellement et la hauteur de prcipitations, comme dans le cas 1 1 1 tracer, defined as: ), asimple mass balance gives composition R 2 autre quantit N2 du mme compos (avec une compo quantit est mlange prsent, est ncessaire, nous devons introduire le taux de traceur , dfini tel que: avec une 18 theisotope ratio of themixture: Rr {18 18base}W = 18Rr18W (4.13) R2 ), un simple bilan de masse donne alors le rapport isotopique du mlange tel que: 18 18 18 18 18 Rr { base} W = Rr W (4.13)

If acomparison is required of, as in our present

tope ratio R1 contain N1/(1 + R1) molecules of

Fig. 4.1. Schematic representation of (A): themixing of two quantities of one compound with different isotopic compositions, and (B): themixing and reaction of two different compounds or two phases of thesame compound with different isotopic composition that will be subjected to isotope exchange and will ultimately become afractionation factor (a) apart.

35

INTRODUCTION

2 0

seawater

Noraor + Nadaad = (Nor + Nad)amix (4.18a) and NorCor + NadCad = (NVariations dabondances isotopiques or + Nad)C mix (4.18b)

()
18

-2 -4

with aknown specific activity f1 1 [1 + Rr (1 + 2 )] + f 2 2 [1 + Rr (1 + 1 )] spcifique connue. aor = 0 = (4.16) aor=0 1 + Rr [ f1 (1 + 2 ) + f 2 (1 + 1 )] N et a sont connues ad= 0 ad Nad and aad are known aor Lactivit spcifique amix doit tre mesure Specific activity amix is to be measured Nad et aad sont connues o (4.16) de 100 / , cette quation peut tre Pour les abondances isotopiques naturelles dans une gamme oo N is unknown and wanted (Eq.4.16a): N est inconnue et recherche (Eq. 4.16a): or or Lactivit spcifique amix doit tre mesure approche ( For 0.03) par:abundances of isotopes within a natural Nor est inconnue et recherche (Eq. 4.16a): aad range of 100 this equation can be approximat(4.19) 1 N or = N ad ed = (to f11within + f22 0.03) by: (4.17) a amix ad N or = a 1 N ad mix ajoute est sanssolution Ifradioactive theadded radioactive is carrier et que donc son activ Si(4.17) la solution support, i.e. Nad = 0,free, = f11 + f22 ce qui signifie quon peut additionner les valeurs avec une trs bonne approximation. La Fig. 4.2 i.e. N =0 and thus thespecific activity a is , ad tend vers , nous devons crire: Si la dans solution radioactive ajoute est sans support, i.e. Nad =ad0, et que donc son activ montre lexemple dun mlange eau degood mer et eau douce un we estuaire. fait dadditionner which means thatentre to avery approximation have Le to write: tend vers , nous devons crire: additivity applies to en values. Fig. 4.2 shows est valable aussi bien pour les teneurs chlorures de leau (traceur conservatif) que pour 18. La = A = N A ad mix mix amix = Nor amix of mixing seawater and river water Aad = Amix = N relation entretheexample les deux est en consquence une ligne droite. mix amix = Nor amix in an estuary. Additivity is valid for theChloride Aad = Amix = Nmix amix = Nor amix and thus: Nor = Aad / amix N or = Aad / amix content of thewater (conservative tracer)ainsi: as well 18 as for . Therelation between thetwo is conseainsi: N or = Aad / a mix Example 2. Determination of an unknown quently astraight line. amount of (human or animal) Example 2. Dtermination dune quantit inconnue de fluide corporel (humain body fluid by adding deuterium ajout deau enriched enrichie deutrium water Example 2. Dtermination duneen quantit inconnue de fluide corporel (humain 4.3.1.1. Isotopic dilution analysis deau enrichie en deutrium Cor mais doit tre calcule partir de 2R ou2 2 de leau du fluide Cajout Apractical application of theprevious section is est connue, or is known; has to be calculated from the R or 2 2 2 Eq. 4.17) nest pas a water of the original fluid en tant que concentration (sang), parce quutiliser theso-called Isotopic Dilution Analysis, amethod Cor est connue, mais doit tre2 calcule body partir de 2R(blood), ou(cf. de leau du fluide because using as aconcentration (cf. used in radiochemistry. By this method an amount 2 Nad est connue mais peut tre nglige (sang), parce quutiliser en tant que concentration (cf. Eq. 4.17) nest pas a Eq.4.17) is not accurate enough of radioactive material can be determined without Cad est connue N est connue mais peut tre nglige ad N is known but may be negligibly small thechemical separation procedures being comad C doit tre mesure mix C est connue ad C is known plete. For instance, if small traces of radioactivity ad N est inconnue etbe recherche ( partir de lquation 4.18b): Cor tre mesure C to measured mix doit are to be quantified, aknown amount of thesame, mix is Nor is unknown and wanted Eq.4.18b): Nor est inconnue et recherche ( partir (from de lquation 4.18b): but inactive compound is added and thechemical C ad separation procedure is carried out (not necessar 1 N ad N or = Fig.4.2 Relation linaire entre concentration en Cl et 18 de leau dans lestuaire dela Western C Cmix ily quantitative). From the final specific activity ad 18 (4.20) = N 1 N ad = 6.5) se Scheldt , quand leau de la rivire Scheldt ra(Cl = 0or(= g/kg); C of thecompound thequantity of belge theoriginal mix 18 = 0). mlange avec les eaux de la then Mer du (Cl = 19,36;3. dioactive compound can be Nord calculated. Example Dtermination dune radioactivit sans support inconnue (Aor) p

(Cl concentration) and 18 of water in the estuary of spcifique. allons mentionner ici quelques mlange. NNous est la quantit respective, C la concentration, A le taux de radioactivit Example 1. Determination ofexemples. an unknown theWestern Scheldt, where water from theBelgian rivquantity/concentration of spcifique. Nous allons mentionner ici quelques exemples. 18 1. Dtermination de la quantit dun produitinacinactif en quantit e er Scheldt (Cl=0 (=g/kg); =6.5)Exemple . Chapitre 4 tiveajout compound by adding aknown inconnues par dune quantit connue du mme Exemple 1. Dtermination de la quantit dun produit inactif en compos quantit av e amount of thesame compound spcifique connue. inconnues par ajout dune quantit connue du mme compos av

Variations dabondances where thesubscripts or, ad and mix isotopiques refer to theoriginal material, theadded material and -6 river water themixture, respectively. N is therespective et N -8 orCor + NadCad = (Nor + Nad)Cmix quantity, C theconcentration, Atheamount of 0 5 10 15 20 radioactivity athespecific we dorigine, au mat N C + N Cadand = (N Cmix activity. o les indices, or, ad et mix se rfrent respectivement auHere matriel or or ad or + Nad) Cl (g/L) briefly mention afew examples. Fig. 4.2. Linear relation between theChlorinity mlange. N estor, la ad quantit la concentration, A le taux de radioactivit o les indices, et mixrespective, se rfrent C respectivement au matriel dorigine, au mat

et

quantit connue du produit inactif (N 3. Determination of an In general, theconservation of mass Example during 3. Example ad)unknown Dtermination dune radioactivit sans support inconnue (Aor) p carrier-free radioactivity (Aor) by theaddition of material requires (cf. Eq.4.15): quantit connue du produit inactif (Nad) (Amix = Aor), tandis que la q Ici lactivit totale, avant et aprs lajout, est la mme adding aknown quantity of theinmlange (Nmix ) est gale la quantit ajoute (Nla ): ad Aor + Aad = Amix or active ( N Ici lactivit totale, avant et aprscompound lajout, est mme (Amix = Aor), tandis que la q ad) 4.4.1.1 ANALYSES DE DILUTION ISOTOPIQUE mlange (Nmix gale la quantit ajoute (Nad): =N A)orest ad amix Une application lAnalyse amix de Dilution Aor = Nad 36 pratique de la partie prcdente est, ce quon appelle, Isotopique, une mthode utilise en radiochimie. Par cette mthode, une quantit de matriel radioactif peut tre dtermine sans que les procdures de sparation chimique soient compltes. Par exemple, si des traces de radioactivit doivent tre quantifies, une quantit connue dun produit identique mais

ABUNDANCE VARIATIONS by NATURAL PROCESSEs

Variations dabondances isotopiques It is common in isotope studies to be concerned with thechange in isotopic composition of ares4.5.1 RESERVOIR AVEC UNE FUITE ervoir because of theremoval 4.5.1 RESERVOIR AVEC UNE FUITEof an increasing Aor = Nadamix (4.21) Un modle fraction une boteof noire rservoir avec une seule fuite est prsent e its dcrivant contents un accompanied by isotope Un modle fractionation. une bote noire dcrivant un rservoir avec une seule fuite est prsent e We will discuss theprocess unN est le nombre total de molcules, et R est le rapport de lisotope rare par rap This method is known as theReverse Isotope der two conditions, (i) removal of acompound N est le nombre total de molcules, et R est le rapport de lisotope rare par rap abondant, tel que Dilution Analysis. =sink) from areservoir without an additional abondant, tel(que N /(1+R(evaporation ) est le nombrefrom de molcules avec lisotope abondant et input a confined water basin N /(1+ R ) est le nombre de molcules avec lisotope abondant et for/(1+ example); removal accompanied by acon4.3.2. Mixing of reservoirs of RN R) est le (ii) nombre de molcules avec lisotope rare stant input (such as evaporation from Chapitre Chapitre 4 4 different compounds RN /(1+ R) est(=source le nombre)de molcules avec lisotope rare alake with ariver input). If themixing process includes chemically differChapitre Chapitre 4 Chapitre4 4 Cette Cette mthode mthode est est connue connue comme comme l Analyse l Analyse Rversible Rversible de de Dilution Dilution Isotopique Isotopique . . ent but reactive compounds of quantities N1 and 4.4.1. Reservoir with one sink N2 with different isotopic compositions R1 and Cette Cette mthode mthode est est connue connue comme comme l l Analyse Analyse Rversible Rversible de de Dilution Dilution Isotopique Isotopique . . Cette mthode est connue comme l Rversible de Isotopique . , the final stage isAnalyse characterised by aDilution fractionR2 Asimple box model describing areservoir with 4.4.2 4.4.2 MELANGE MELANGE DE DE RESERVOIRS RESERVOIRS AVEC AVEC DIFFERENTS DIFFERENTS COMPOSES COMPOSES only one sink. is presented by Fig.4.3. Here N is ation between thecompounds. During there acSi4.4.2 Si le le processus processus dede mlange mlange implique implique des des composs composs ractifs ractifs mais mais chimiquement chimiquement diffrents diffrents enen quantit quantit 4.4.2 MELANGE MELANGE DE DE RESERVOIRS AVEC AVEC DIFFERENTS COMPOSES thetotal number of molecules, and R is theratio 4.4.2 MELANGE DE RESERVOIRS RESERVOIRS AVEC DIFFERENTS DIFFERENTS COMPOSES tion achemical shift between thetwo compounds COMPOSES N1N et et N N et et avec avec des des compositions compositions isotopiques isotopiques diffrentes diffrentes R R et et R R , le , le stade stade final final est est caractris caractris par par un un 1 2 2 1 1 2 2 of therare to abundant molecular concentrations, will often occur. Thequantities change into N Si Si le le processus processus de de mlange mlange implique implique des des composs composs ractifs ractifs mais mais chimiquement chimiquement diffrents diffrents en en quantit quantit 1 Si le processus de mlange implique des composs ractifs mais chimiquement diffrents en quantit fractionnement fractionnement entre entre ces ces composs. composs. Durant Durant cette cette opration, opration, unun dplacement dplacement chimique chimique entre entre les les deux deux so that with isotopic compositions of R1 11 and R anddes N N N et N N et avec avec compositions isotopiques isotopiques diffrentes diffrentes R R et et R ,, le le stade stade final final est est caractris caractris par par un 11 et 22 et 22 N avec des des2compositions compositions isotopiques diffrentes R et R R ,2 le est caractris par un un 1 et N2 et 1vers 2 Fig.4.3 Reprsentation schmatique du processus de Rayleigh. N est le nombre d composs composs interviendra interviendra souvent. souvent. Les Les quantits quantits voluent voluent vers N N ' ' stade et N N ' 2final avec ' avec des des compositions compositions 1 1et 2 where thelatter values are afractionation factor N /(1+ R) is thenumber of abundant isotopic molfractionnement fractionnement entre entre ces ces composs. composs. Durant Durant cette cette opration, opration, un un dplacement dplacement chimique chimique entre entre les les deux deux fractionnement entre ces composs. Durant cette opration, un dplacement chimique entre les deux Fig.4.3 Reprsentation schmatique du total processus de Rayleigh. N est nombre d lisotope abondant (prs. nombre de molcules), R est le le rapport iso isotopiques isotopiques R1R ' et 'apart. et R2R ', 2ces ',An ces dernires dernires valeurs valeurs tant tant dfinies dfinies auau facteur facteur dede fractionnement fractionnement prs. Une Une 1 ecules and example is theexchange between gascomposs composs interviendra interviendra souvent. souvent. Les Les quantits quantits voluent voluent vers vers N N ' ' et et N N ' ' avec avec des des compositions compositions 1 1 2 2 composs interviendra souvent. Les quantits voluent vers bicarbonate, N N2' avec despar compositions lisotope abondant ( nombre total( de molcules), R est le rapport iso 1' etfacteur de fractionnement impliqu lquilibre ou cintique). ide ide dede cece mlange mlange est est lchange lchange entre entre unun CO CO gaz et et une une solution solution bicarbonate, comme, comme, par exemple, exemple, 2 gaz 2solution abicarbonate as, for ineous CO 2 and RN /(1+ R ) is thenumber of rare isotopic molisotopiques isotopiques R R ' ' et et R R ', ', ces ces dernires dernires valeurs valeurs tant tant dfinies dfinies au au facteur facteur de de fractionnement fractionnement prs. prs. Une Une 1 1 2 2 isotopiques R ' et et ces dernires valeurs tant dfinies au facteur de fractionnement Une facteur de fractionnement impliqu ( lquilibre ou cintique). 1 2',CO leau leau dun dun lac lac et le R le CO ouand ou le le mlange mlange dune dune eau eau douce douce et et dune dune eau eau deprs. de mer mer 2 atmosphrique, 2 atmosphrique, stance, between lake water atmospheric CO 2, ecules ide ide de de ce ce mlange mlange est est lchange lchange entre entre un un CO CO gaz et et une une solution solution bicarbonate, bicarbonate, comme, comme, par par exemple, exemple, 22 gaz ide de ce mlange est lchange entre un CO gaz et une solution bicarbonate, comme, par exemple, 2 diffrents diffrents pH. pH. or themixing of fresh and seawater with different leau leau dun lac et et le le CO CO atmosphrique, ou ou le le mlange mlange dune dune eau eau douce douce et et dune dune eau eau de de mer mer 22 atmosphrique, Forde theremoval of dN molecules with an accom- associ , le bila Lors de la perte dN molcules avec un facteur de fractionnement leau dun dun lac lac et le CO atmosphrique, ou le mlange dune eau douce et dune eau de mer 2 pH.identique Un Un bilan bilan de de masse masse identique pour pour lisotope lisotope rare rare peut peut tre tre crit crit (Fig. (Fig. 4.1B): 4.1B): diffrents diffrents pH. panying factor , themass balance associ , le bila Lors de la perte de dNfractionation molcules avec un facteur de fractionnement lisotope rare donne: diffrents pH. pH. Asimilar mass balance for therare isotope can be rarefor therare isotope gives: lisotope donne: 'N N ' identique ' R2R 'N N 'pour R N N1 Rrare R N N Un Un bilan de masse masse identique pour lisotope lisotope rare peut peut tre tre crit (Fig. 4.1B): 1R 1'1 1 2'2 2' R 11 22 2 Un bilan bilan de deR masse identique pour lisotope peut tre crit crit (Fig. (Fig. 4.1B): 4.1B): + + ==1 + + 2rare written (Fig.4.1B): R R R+dR 1+ 1+ R1R ' 1' 1 + 1+ R2R ' 2' 1+ 1+ R1R1 1 + 1+ R2R2 (N + d N ) dN N= R R ' ' N N ' ' R R ' ' N N ' ' R R N N R R N N 1 1 1 1 2 2 2 2 1 1 1 1 2 2 2 2 + R R d R RR R1 ' N1 ' + 1+ R N = 1+ R + d R (N + d N ) 1+ + R2 ' N 2 ' = = R1 N1 + + R2 N 2 or dN + = + 1 1+ +R R ' 1 1 + +R R22''' 1 1 + +R R 1 1 + +R R22 11'' 11 + + + + 1 R 1 R d R 1 R 1 + R 1 + R 1 + R 1 + R 1 2 1 2 'N 'N '+ +2R 'N 'N ' 1R N11N + +2R N22N2 (4.22) (4.22) ouou R1R 11 1' R 22 2' R 1R To agood approximation we will furthermore Pour une bonne approximation, nous considrerons, pourequal la suite du paragraphe, que take thetotal number of molecules to R N R + R N R R N R (4.22) 1 1 2 2R 1+ 1 + 2N2 ' N ' N ' ' + + R ' N ' N ' ' N N + R R N N (4.22) (4.22) ou ou R R Pour une bonne approximation, nous considrerons, pour la suite duen paragraphe, que 1 1 1 1 2 2 2 2 1 1 1 1 2 2 2 2 de molcules est gal au nombre de molcules de lisotope abondant: fait, pour cett 'N '1 + 'N2 ' R1mmes N1 + R N2 (4.22) ou N1N RN 1 2approximations thenumber of abundant isotopic molecules: in '+ + 2N '= = N + N +R N ,2et les les mmes approximations que que celles celles appliques appliques dans dans lquation lquation 4.15 4.15 pour pour avec avec 1' N 2' 1 1 2 2, et de molculesfact, est gal nombre de molcules de lisotope abondant: fait, cett where N1+ N2 = N1 + N2, and thesame approxiseront gaux 1+ R (ce qui ne revient pas aupour mme forau this approximation all denominators are en la la gamme gamme des des valeurs valeurs dede de de tous tous les les chantillons chantillons naturels. naturels. tous les dnominateurs ' ' + + N N ' ' = = N N + + N N , , et et les les mmes mmes approximations approximations que que celles celles appliques appliques dans dans lquation lquation 4.15 4.15 pour pour avec avec N N mation applies as in Eq.4.15 for therange of tous les dnominateurs seront gaux 1+ R (ce qui ne revient pas au mme 1 1 2 2 1 1 2 2 taken equal 1+ (which is not thesame as necompltement R!). Le bilan deR masse lisotope rare devient maintenant: appliques dans lquation 4.15pour pour avec N1' + N2' = N1 + N2, et les mmes approximations que celles Ceci Ceci conduit conduit : values : of all natural samples. glecting R completely!). Themass balance for la la gamme gamme des des valeurs valeurs de de de de tous tous les les chantillons chantillons naturels. naturels. compltement R !). Le bilan de masse pour lisotope rare devient maintenant: la gamme des valeurs de de tous les chantillons naturels. RN = (R + dR)(N + dN)becomes: RdN therare isotope now R N N + +in: R N N2 This results Ceci Ceci conduit : : R1 RN = (R + dR)(N +(4.23) dN) RdN 11 1 R 2 22 Ceci conduit conduit R2: R '= et et R1R '= =R 2R ' 2' et, en ngligeant produits de diffrentielle: 2 '= 1 ' RN les = (R + dR)( N lquation +(4.23) dN) R dN N 1N '+ ' N + N ' ' 1 2 2 R N R N R N + R N + et, en ngligeant les produits de lquation diffrentielle: 11 N 11 + R 22 N22 R 2 2 R22'''= = 1 1 R et et R = = R R22'' (4.23) (4.23) (4.23) and and theproducts of differentials: 11'' R et R R /N (4.23) d R/Rneglecting = ( 1)dN 2 = 1 ' = R2 ' N N11'+ '+N N22'' ouou N 1 '+ N 2 ' NN /N d dR R//R R= =( (1)d 1)d /N Lintgration et lapplication des conditions aux limites: R = Ro at N = No (rien na t or ou ou ou f1 f 2 f1 'f f1+ f 22 Lintgration et lapplication conditions aux limites: R = Ro at N = No (rien na t Integration anddes applying 1 + 2 1 ' ' '+ '+ prsent) 2 et et 1 2 ' (4.24) (4.24) theboundary condition: and (4.24) donnent: 2 ' 1 ' 2 R = Ro at N = No (nothing has been neglected yet) f1 'f 1+ 1+ ' prsent) donnent: ff + ff2 ff11'' 11 + 1 2 22 f11 gives: 1 1 1 + f 2 2 f1 ' ' ' et et ' ' ' + ' + (4.24) (4.24) 22 22 et 11 (4.24) 2 ' f =N 1 ' 2 '+ R N 1 1 1 + + ff '' with N N ), et cetera. 11'+ 1 1/( 2 1 + f = 1 = 1N /(1 N /(1N + N + N ), et ), et cetera. cetera. avec avec f1 = f1 N N 1 2 2 R N0 R 0 = (4.25a) These equations are applied to theindirect deter 18 18 R N 0 0 dun chantillon chantillon deau, deau, via via la la mesure mesure Ces Ces quations quations sont sont appliques appliques la dtermination dtermination indirecte indirecte dede dun = = N N /( /( N N + + N N ), ), et et cetera. cetera. avec avec f f 18 la 1 1 1 1 1 1 2 2 of awater sample, viz. by measurmination of cetera. avec f1 = N1/(N 1 + N2), et 18 18 du du CO CO quilibrant avec avec leau leau plutt plutt que que via via leau leau elle-mme elle-mme (Sect. (Sect. 10.2.1.1 et et 11.2.3.4). 11.2.3.4). dudu 18 par rapport aux rfrences standardises: refou, avec les valeurs 2 quilibrant 2 18 18 of CO with thewater rather ing or10.2.1.1 in values with respect to thestandardised 2 equilibrated 18 dun dun chantillon chantillon deau, deau, via via la mesure mesure Ces Ces quations sont appliques la dtermination indirecte de dun chantillon deau, via la la mesure Ces quations quations sont sont appliques appliques la la dtermination dtermination indirecte indirecte de de par rapport aux rfrences standardises: ou, avec les valeurs thewater itself andelle-mme 11.2.3.4).(Sect. erence: 18 18 du du CO COthan quilibrant quilibrant avec avec leau leau(Sect.10.2.1.1 plutt plutt que que via via leau leau elle-mme (Sect. 10.2.1.1 10.2.1.1 et et 11.2.3.4). 11.2.3.4). du du 18
22 quilibrant avec leau plutt que via leau elle-mme (Sect. 10.2.1.1 et 11.2.3.4). du du CO 2 4.5 4.5 CHANGEMENTS CHANGEMENTS ISOTOPIQUES ISOTOPIQUES DANS DANS LE LE PROCESSUS PROCESSUS DE DE RAYLEIGH RAYLEIGH

Here thetotal amount of activity before and after theaddition is thesame (Amix=Aor), while thefinal quantity of mixture (Nmix) is equal to thequantity added (Nad):

4.4. Isotopic changes in Rayleigh processes Variations dabondances isotopiques

Il 4.5 Il est est courant courant dans dans les les tudes tudes isotopiques isotopiques dtre dtre confront confront des des changements changements dede composition composition 4.5 CHANGEMENTS CHANGEMENTS ISOTOPIQUES DANS LE PROCESSUS DE RAYLEIGH 4.5 CHANGEMENTS ISOTOPIQUES ISOTOPIQUES DANS DANS LE LE PROCESSUS PROCESSUS DE DE RAYLEIGH RAYLEIGH isotopique isotopique dans dans unun rservoir rservoir enen raison raison dede la la perte perte dune dune partie partie croissante croissante dede son son contenu, contenu, perte perte Il Il est est courant dans dans les les tudes tudes isotopiques dtre dtre confront confront des des changements de de composition Il est courant courant dans les tudes isotopiques isotopiques dtre confront des changements changements de composition composition accompagne accompagne par par unun fractionnement fractionnement isotopique. isotopique. Nous Nous allons allons discuter discuter de de cece processus processus sous sous deux deux isotopique isotopique dans dans un un rservoir rservoir en en raison raison de de la la perte perte dune dune partie partie croissante croissante de de son son contenu, contenu, perte perte isotopique dans un rservoir en raison de la perte dune partie croissante de son contenu, perte conditions, conditions, (i)(i) la la perte perte dun dun compos compos (=(= fuite fuite ) depuis ) depuis unun rservoir rservoir sans sans apport apport additionnel additionnel (vaporation (vaporation accompagne accompagne par par un un fractionnement fractionnement isotopique. isotopique. Nous Nous allons allons discuter discuter de de ce ce processus processus sous sous deux deux

37

Rpar R d NLintgration N quation d N donne: = lquation = ou R est donn 3.25a. de cette 1 N0 N

N

N0 N N
N N

0 0 0 ou R est donn 3.25a. Lintgration donne: = lquation = R0 de cette quation R0 Rpar

N INTRODUCTION N 0 N

N N 0

1 (N / N ) 1 N / N0 1 (N / N 0 ) 1 N / N0

= (1 + 0)(N/N0) 1

ou

(4.25b)

N N0 R0 R = N or N 0 N 0

N0 N

= R0

where N/No represents theremaining fraction of 1 (N / N 0 ) ( ) 1 = 1 + ou (4.27) 0 theoriginal reservoir; Ro and 0 refer to theorigi1 N / N0 nal isotopic composition. Once more we have to remind thereader that (= 1) is asmall numTheresulting change in e (for 0 = 0) is shown in ( ) N / N0 1 ( ) 0de 1est montr sur la Fig. 4.4 par la courbe inf = 1 +by e (pour 0) Le changement rsultant 0 = ber, for instance 0.004 if thefractionation is Fig.4.4 thelower line. 1 N / N0 4.

La composition isotopique moyenne du compos form (= somme (contributions ) des incrments) un temps fractionnes La composition isotopique isotopic moyenne composition du compos form (= somme ()ddes un temps Theaverage of theformed R incrments) d par N rapport au prlvement total (f1 + f2 = 1). donn est: ( = 1 f1 + 2 f 2 1) donn est: compound (=of thesum (S) of theincrements) at R N ce qui, aprs intgration, donne: acertain timeNis: N ce qui, aprs which intgration, afterdonne: integration gives: R0 N 00 1 N0 1 1 0

4.5.2 RESERVOIR AVEC DEUX FUITES Theincrease in 18O/16O of a confined 4.4.2. Reservoir two sinks = 0) estChapitre montr sur la Fig. 4.4 par la courbe inf Le water changement rsultant de e (pour 0 with 4 body by evaporation with < 1 (Fig. 4.4: upUn phnomne lgrement plus compliqu, quoique fait raliste, se produit si Aslightly more complicated, but tout nevertheless per curve) serves as an example of thisretirent simplesimultanment deux composs diffrents au rservoir considr (Fig. 4.5 realistic phenomenon occurs if two processes si4.5.2 by RESERVOIR AVEC DEUX FUITES Rayleigh process. Another case is presented intervient quand, lors de la croissance algues la surface de leau, le pH de ladit multaneously withdrawdes two different compounds the13C/12C increase in lake-water bicarbonate due Un phnomne lgrement plus compliqu, quoique tout deux occurs faitprocessus raliste, se produit si from thereservoir (Fig.4.5). This process provoquant la formation de carbonate de calcium. Les impliquent to thegrowth of plankton. retirent simultanment deux composs au(spcifiques). rservoir considr (Fig. 4.5 when, through growth of diffrents algae in surface water, facteurs de fractionnement du carbone caractristiques We have now focussed our attention on intervient theiso- quand, lorsof de thewater la croissance des algues la surface de leau, le pH de ladit thepH increases causing theformaLe bilan de masse pour lisotopie rare donne donc: processes topic change of thereservoir. It is also relevant tion of calcium carbonate. Both provoquant la formation de carbonate de calcium. Les deuxhave processus impliquent to calculate theisotopic composition of thecomcharacteristic isotope fractionation infacteurs de fractionnement du carbon carbone caractristiques (spcifiques). = (R + dR)(N + dN) 1Rf1dN 2Rf2dN pound which is gradually built up by the infini- RN volved. Le addibilan de masse pour lisotopie rare donne donc: tesimal increments dN. This is not asimple Therare isotope mass balance now gives: tive procedure, because theisotopic composition Ici f1 + f2 = 1: une quantit totale dN de llment considr est prleve du rservoir. = (Ravons: + dR)(N + dN) 1Rf1dN 2Rf2dN of thereservoir changes during theprocess and RN cas prcdents, nous RN = (R + dR)(N + dN) 1Rf1dN 2Rf2dN thus also that of theincrements dN. An example Fig.4.5 Reprsentation schmatique du processus de Rayleigh dans deux is found in theformation ofdabondances acarbonate deposit Here f1+f2 =totale 1: atotal amount dN of theelement dN de llment considr est prleve dulequel rservoir. Ici f1 + f2 = 1: Variations isotopiques dune R quantit dN Fig.4.5 Reprsentation schmatique du processus de Rayleigh( dans lequel deux dabondances isotopiques from agroundwaterVariations mass which looses CO when ( ) f f 1 = + under consideration is removed from thereseret ); f prlevs du rservoir avec diffrents fractionnements 2 1 1 2 2 1 2 1 et f2 cas prcdents, nous avons: R N et prlevs rservoir avecpar diffrents fractionnements (1 (f exposed to theatmosphere. voir. As du with theprevious case, we have: 2); f1 et f2 contributions fractionnes rapport au prlvement total 1 + f2 = 1).

Chapitre 4

1 f1 + 2 f 2 N N 0 1 ( N / N 0 ) N = (1 + 0 )(N / N 0 ) (4.28b) (4.26) R0 R = N 0 N N 0 = R0 1 ( N / N 0 ) 1 f1 + 2 f 2 0 N = (1 + 0 )(N / N 0 )(4.26) = R0 1 N / N 0 R = N 0 N R0 N0 N 1 N / N 0 This reduces to thesimple case of one sink N0 N N0 (4.26) Cette solution rduit le problme un cas simple de prlvement unique (Eqs. 4.25a (Eqs 4.25a and 4.25b) if f2 =0, while theexpoCette solution rduit le problme un cas simple de prlvement (Eqs. 4.25a ou cas ou f2 = 0,nent tandis que la fonction exposant se rduit 1f1 siunique le prlvement du reduces to 1f1 ifen theremoval of thesecond ou cas ou f = 0, tandis que la fonction en exposant se rduit f si le prlvement du 2 1 1 compound occurs without fractionation. se fait sans fractionnement. se fait sans fractionnement. 1 ( N / N ) = (1 + 0 )1 (N / N 0 (4.27) 0 ) 1 = (1 + 0 ) 1 N / N 1 (4.27) 4.5.3 RESERVOIR AVEC UNE SOURCE UNE FUITE, FONCTION D 0 4.4.3. Reservoir with one ET source 1 N / N0 4.5.3 RESERVOIR AVEC UNE SOURCE ET UNE FUITE, FONCTION D and one sink, as afunction Bien que les paragraphes prcdents prsentent des exemples pratiques du processus of time prsentent des exemples pratiques du processus Bien que paragraphes prcdents Fig. 4.4 les par la courbe infrieure. Le changement rsultant de e (pour 0 = 0) est montr sur la cas gnral inclus lexistence dune seule source et dun seule fuite. Ils sont reprse Fig. 4.4 par la courbe infrieure. Le changement rsultant de e (pour 0 = 0) est montr sur la cas gnral inclus lexistence dunede seule source dun fuite. Ils sont reprse Although theprevious are practical examples of perte dapport i (en quantit par unit temps) et et par un seule taux de u (Fig. 4.6A Rayleigh processes, thegeneral case includes dapport i (en quantit par unit de temps) et par un taux de perte u (Fig. 4.6A 4.5.2 RESERVOIR AVEC DEUX FUITES fractionnement lapport, i, nest pas ncessairement gal lunit. 4.5.2 RESERVOIR AVECrepresentation DEUX FUITES theexistence of asource as well as asink. These Fig. 4.3. Schematic of the Rayleigh fractionnement lapport, i, nest pas ncessairement gal lunit. Un phnomne lgrement plusnumber compliqu, quoique tout fait raliste, se represented produit si deux processus Le bilan de lisotope rare est: are by asupply rate i (in quantity per process. N is the of abundant isotopic mol -de masse Un phnomne lgrement plus compliqu, quoique tout fait raliste, se produit si deux processus Le bilan de masse de lisotope rare est: rate u (Fig. retirent simultanment deux composs diffrents R au considr 4.5). processus unit (Fig. time) andCe aloss 4.6A), while ecules ( total number of molecules), is rservoir theisotope retirent simultanment deux composs diffrents au rservoir considr (Fig. 4.5). Ce processus ( ) ( ) RN + R i d t = R + d R [ N + i u d t ] necessarily + Ru d t i i input, i, is not ratio, is (equilibrium kinetic) intervient quand, lors de the la croissance des or algues la fractionation surface de leau, thefractionation le pH de ladite eauwith augmente, ( ) ( ) RN + R i d t = R + d R [ N + i u d t ] + Ru d t intervient quand, lors de la croissance des algues la surface de leau, le pH de ladite eau augmente, i i equal to unity. factor involved. provoquant la formation de carbonate de calcium. Les deux processus impliquent par ailleurs des partir duquel nous avons, par sparation des variables (avec 1 = ): provoquant la formation de carbonate de calcium. Les deux processus impliquent par ailleurs des facteurs de fractionnement du carbone caractristiques (spcifiques). partir duquel nous avons, par sparation des variables (avec 1 = ):

N 1 f1 + 2 f 2 1 N R = R0 N N N R = R0 N0 0 where R is given by Eq.3.25a. Integration of this ou R est donn par lquation 3.25a. Lintgration de cette quation donne: ou ou R est donn par lquation 3.25a. Lintgration de cette quation donne: equation gives: or ou
1

R d N = 1 R = R 1 01 R d N = N 0 N N R = N 0 N N 1 N0 N N N0 N N

N N

dN dN

1 f1 + 2 f 2 1

(4.28a)

facteurs de fractionnement du carbone caractristiques (spcifiques). Le bilan de masse 38 pour lisotopie rare donne donc: Le bilan de masse pour lisotopie rare donne donc: RN = (R + dR)(N + dN) 1Rf1dN 2Rf2dN RN = (R + dR)(N + dN) 1Rf1dN 2Rf2dN

dR dt = d R du t )(t t ) (i + u )R i Ri i = N 0 + (i 0 (i + u )R i Ri i N 0 + (i u )(t t 0 )

ou N au temps t a t remplac par le dnominateur droite (N = N0 t = t0).

Fig.4.5 Fig.4.5

Reprsentation schmatique du processus de Rayleigh dans lequel deux composs sont Reprsentation schmatique du processus de Rayleigh dans lequel deux composs sont prlevs du rservoir avec diffrents fractionnements (1 et 2); f1 et f2 se rfrent aux prlevs du rservoir avec diffrents fractionnements (1 et 2); f1 et f2 se rfrent aux contributions fractionnes par rapport au prlvement total (f1 + f2 = 1). contributions fractionnes par rapport au prlvement total (f1 + f2 = 1).
ABUNDANCE VARIATIONS by NATURAL PROCESSEs

ce qui, aprs intgration, donne: ce qui, aprs intgration, donne:

N 1 f1 + 2 f 2 1 N R=R R = R0 N0 0 N 0
ou ou
= (1 + 0 )(N / N 0 ) )(N / N 0 ) = (1 + 0
1 f1 + 2 f 2 1 f1 + 2 f 2

1 f1 + 2 f 2 1

(4.28a) (4.28a)

(4.28b) (4.28b)

Cette solution rduit le problme un cas simple de prlvement unique (Eqs. 4.25a et 4.25b) dans le Fig. 4.5. Schematic representation of the Rayleigh Cette solution rduit le problme un cas simple de prlvement unique (Eqs. 4.25a et 4.25b) dans le cas ou f2 = 0, tandis que la fonction en exposant se rduit 1f1 si le prlvement du second compos process where two compounds cas ou f2 = 0, tandis que la fonction en exposant se rduit 1f1 si le prlvement du second compos are being removed from se fait sans fractionnement. thereservoir with different fractionation (1 and 2); f1 se fait sans fractionnement. Fig. 4.4. he enrichment of a rare heavy isotope in and f2 refer to thefractional contributions to thetotal a reservoir by the Rayleigh process as a function of sink (f1 + f2=1). 4.5.3 RESERVOIR AVEC UNE SOURCE ET UNE FUITE, FONCTION DU TEMPS the fraction removed. TheSOURCE preferential of FONCTION DU TEMPS 4.5.3 RESERVOIR AVEC UNE ET removal UNE FUITE, light isotopic species is accompanied by a frac Bien que les the paragraphes prcdents prsentent des exemples pratiques du processus de Rayleigh, le Bien que les paragraphes prcdents prsentent des exemples pratiques du processus de Rayleigh, le tionation of < 1. The lower line present the aver cas gnral inclus lexistence dune seule source et dun seule fuite. Ils sont reprsents par un taux cas gnral inclus lexistence dune seule source et seule fuite. Ils sont reprsents par un taux age cumulative composition of dun thecompound dapport i (en quantit par isotopic unit de temps) et par un taux de perte u (Fig. 4.6A), alors que le dapport i (en quantit par unit de temps) et par un taux de perte u (Fig. 4.6A), alors que le formed by theprocess, S (Eq.4.26). fractionnement lapport, i, nest pas ncessairement gal lunit. fractionnement lapport, i, nest pas ncessairement gal lunit. Le bilan de masse de lisotope est: Therare isotoperare mass balance is: Le bilan de masse de lisotope rare est:

RN + R i d t = (R + d R )[N + (i u )d t ] + Ru d t RN + ii Rii i d t = (R + d R )[N + (i u )d t ] + Ru d t

1 = ): partir duquel nous avons, we par sparation des variables (avec from have by separation of variables 1 = ): partir duquel nouswhich avons, par sparation des variables (avec

(with - 1= ): dR dt dR dt = (i i + u )R i Ri i = N 0 + (i u )(t t 0 ) ( + u )R i Ri i N 0 + (i u )(t t 0 )

where at atime has been replaced by (thedeou N au temps t a tN remplac part le dnominateur droite N = N0 t = t0). ou N au temps t a t remplac par le dnominateur droite (N = N0 t = t0). Variations Chapitre 4 Rayleigh nominator on theright (N=dabondances N0 at t=t0).isotopiques Fig. 4.6. Schematic representation of the 60 60 process with one source and one sink (A) as afuncIntegration and applying theboundary condition of time with n and m denoting theinput and output Lintgrationthat et lapplication aux limites telles que R = R0tion t= t0 conduisent :i R = tconditions R = R0 at tdes i Ri i (i / N 0 )(t t0 ) 0 results in: R R = + rates respectively, and (B) Variations dabondances isotopiques 0 e as afunction of thequanti i + u ties of in- and outflow with determining the relation i u between input and output rates. i Ri i Ri i u ( ) + R0 1 + t t (4.29) R= 0 des conditions aux limites ( tu =/ti0) conduisent 0+ N 0:Comme 1 + (telles u / i )queR = R1 t , une situation dquilibre est atteinte avec:
i + u i u

oui u. i u dans le cas i Ri (t t 0 ) + R0 1 + +u (,ule / ibilan ) de masse N 0 est: Si i1=

(4.29) (4.29)

R=

i Ri

ou

(1 + i ) (1 + i )
1+

(4.31)

for0 thecase iR )N u. RN + iRiidt where = (R + d 0 + Rudt If i=u, themass balance is:

Chapitre 4

ce qui peut tre approch par: = i + (i )

which is approximated by

+( i ) (4.32) = i se Une telle situation produit quand lvaporation du lac est contrebalance par lappo

(R + dR)N0 + Rud t 0 + iRiidt = (R + dR)N0 + Rudt RN

from which we can similarly derive:

R=

i Ri R + R0 i i e (i / N

)(t t0 )

Un autre exemple important est fourni par lvapotranspiration (eau du sol prleve p As t , asteady-state situation is reached with: congruent dissolution process which occurs in Comme t , une situation dquilibre est atteinte avec: travers de laction capillaire des ses vaisseaux, et subsquemment vapore au niveau feuilles) qui provoque le transport de leau par la plante depuis le sol jusque fractionnement isotopique net. Ce processus est dmontr en Fig. 39 4.7. (1 + i ) (1 + i ) R R = i i ou = (4.31) 1+ Le faible diamtre des capillaires implique un flux relativement lev. Ceci est esse empche leau isotopiquement lourde des feuilles de diffuser vers le bas. (4.32) ce qui peut tre approch par: = i + (i )

une rivire (Mer Morte, Lac Titicaca, Lac Tchad). Dans ce cas, i = 1 parce que l Such asituation occurs where theevaporation doivent sans fractionnement. signification la valeurof de of alakeLa is balanced by et theinflow water from tre considres processus dcrit galement le phnomne de dissolution incongruente qui se produ ariver (Dead Sea, Lake Titicaca, Lake Chad). In systmes deaux Le rsultat est compris simplement theinflow occurs withouten notant quun r this souterraines. case i=1 because (4.30) (4.30) ncessite desfractionation. apports isotopiquement quivalents aux pertes Ri = R). Themeaning and value of ( has to

be considered separately. It also describes thein-

Ceci conduit une quation diffrentielle: RN + iRi(1 f)dN = (R + dR)(N + dN) RfdN

1)R + (1 f ) i Ri N dR dN = Lintgration ( et conditions 1)R + (1 des flapplication f ) N aux limites avec R = Ro quand N = No con i Ri
INTRODUCTION

d R diffrentielle: dN Ceci conduit une quation =

(f

fR 1 = Ro quand N = No con et lapplication des conditions aux limites avec some groundwater systems. Theresult isLintgration simply ( ( 1 f ) i 1 f ) i N understood by noting that steady state requires R= Ri + R0 Ri 1 f 1 f N 0 f 1 theinput to be isotopically equal to theoutput (1 f ) i R + R (1 f ) i R N R= (4.33) (Ri=R). i i 0 1 f 1 f N0 exemple courant de ce p ou N/N0 indique la fraction restante du rservoir originel. Un where N/N0 denotes theremaining fraction of Another important example is thefact that evapo nature est reprsent par lvaporation partir dun rservoir deau isol. Avec une ta transpiration (thephenomenon that water from theoriginal reservoir. Acommon example of this fraction restante du rservoir originel. Un exemple courant de ce p ou N/N 0 indique de ce rservoir, Rla approche: thesoil is taken up by aplant through capillary process in nature is represented by theevaporanature est reprsent par lvaporation partir dun rservoir deau isol. Avec une ta action of theplant vessels, and subsequently tion of an isolated water body. With decreasing de ce rservoir, R approche: (1 f ) i evaporates from theleaf surface) causes water to size N, R approaches: R =of thereservoir 1 f be transported by aplant from thesoil to theair (1 f ) i with no net isotope fractionation. Theprocess is R = (4.34) 1 f demonstrated by Fig.4.7.

Fig.4.7

surface de la feuille, lvaporation est accompagne dun fractionnement Av/l (Table 7.3 Sect.4.4.1. ou 7.4). En tat stationnaire, la vapeur deau qui schappe devrait avoir la mme valeur R que leau transpire. Le rsultat est que leau de la feuille (suppose bien mlange) est
18 4.4.4. en Reservoir with one source enrichie O et 2H par v/l.

des teneurs en H et O le longreservoir de son cours; reprsente lvaporation et lchang of awell-mixed are balanced such that If thesink is absent, theisotopic composition ap- en une rivire rgion tropicale, o lvaporation est significative et produit une augme atmosphrique; I0 est le fluxcomposition deau originelle la source de la rivire. theisotopic of thereservoir comproaches for t to R=iRi. 2 18 des teneurs en H et O le long de son cours; reprsente lvaporation et lchang pound has become inapports time (Fig. Ltat stationnaire ncessite que les constant fuites et les soient4.8). quilibrs, aussi bien p In thegeneral cases where i u, (for instance, atmosphrique; I0 est le flux deau originelle la source de la rivire. Apractical example of this model is presented rares que pour les isotopes abondants. Cette condition est mathmatiquement reprsen slowly increasing or decreasing surface water Ltat stationnaire ncessite que les fuites et les apports soient quilibrs, aussi bien p by ariver in atropical region where evaporation bodies in which cases i=1), theresulting iso2 rares que pour isotopes abondants. conditionincreasing est mathmatiquement reprsen isles significant, resultingCette in gradually dabondances isotopiques topic composition Variations of thereservoir depends on 18 and values along thecourse of theriver; repthecompetition between sink and source. If resents theevaporation and exchange with atmou < i and for t schmatique , R approaches iRidvapotranspiration. [1 + (u/i)], Reprsentation du processus Le flux capillaire de leau spheric vapour; I0 is theoriginal water flow rate at 18 R 2 , as while in theopposite case ( u > i ): du sol, de rapport isotopique Ri (for O or H), se produit sans fractionnement. A la theriver source. with thesimple Rayleigh process discussed in

Thesmall diameter of thecapillary results in a relatively high flow rate. This is essential, be- FRACTIONNEMENT 4.4.5. Reservoir with two sources 4.5.5 RESERVOIR AVEC DEUX SOURCES ET DEUX FUITES, AVEC E cause it prevents theisotopically heavy leaf water Enfin, nous allons traiter des conditions en tat stationnaire, and two sinks, with and i.e. situation dans laquell FRACTIONNEMENT to diffuse downward. et sortant dun rservoir bien mlang sont quilibrs de telle faon que la compositi without fractionation Enfin, nous allons traiter des conditions en tat stationnaire, i.e. situation laquell constante dans le temps (Fig. 4.8). Un exemple pratique de dans ce modle e If there is no source, i=0 and Eq.4.29 rservoir reduces reste Finally we will treat theconditions at astationet sortant dun rservoir bien mlang sont quilibrs de telle faon que la une compositi une rivire en rgion tropicale, o lvaporation est significative et produit augme to Eq.4.25a, thesimple case with only one sink. ary state, i.e. asituation in which in- and outflow

4.5.5

RESERVOIR AVEC DEUX SOURCES ET DEUX FUITES, AVEC E

2 18 dans le temps (Fig. 4.8). Un exemple pratique de ce modle e rservoir reste constante

and one sink, s afunction of mass

4.5.4

If theRayleigh process involves one and FONCTION DE LA MASSE RESERVOIR AVEC UNE SOURCE ETsource UN FUITE, one sink there is an alternative mathematical ap-

Si le processus de Rayleigh met en jeu unecomposition source et une proach in which theisotopic isfuite, con- on a une approche mathmatique alternative dans laquelle la composition isotopique est considre comme une fonction du changement sidered to be afunction of changes in quantity N , de quantit Nrather plus que comme une(Fig.4.6B). fonction du temps (Fig. 4.6B). Le bilan de masse isotopique donne than of time Theisotope mass balance now gives: donc: Fig. 4.7. Schematic representation of theevapotransRN iR i(1 f)dN = (R + dR)(N + dN) RfdN piration process. The capillary flow of the soil water RN+ + iRi(1 f)dN = (R + dR)(N + dN) RfdN with isotope ratio Ri (for 18O or 2H) occurs without Ceci conduit une quation diffrentielle: This results in thedifferential equation: fractionation. At thesurface of theplant leaf evaporadR dN tion is accompanied by fractionation Av/l (Table7.3 or = 7.4). In astationary state theescaping vapour should (f 1)R + (1 f ) i Ri N have thesame R value as thetranspired water. ThereN is =N : LintgrationIntegration et lapplication des conditions of aux limites avec R con= Ro quand and application theboundary sult that the (supposedly well-mixed) leaf water is o conduit 18 2 enriched in O and H by v/l. dition that R = Ro at N = No results in:

40

(1 f ) i R R=
1 f

(1 f ) i R N + R0 i 1 f N0

f 1

(4.33)

ou N/N0 indique la fraction restante du rservoir originel. Un exemple courant de ce processus dans la nature est reprsent par lvaporation partir dun rservoir deau isol. Avec une taille dcroissante

ABUNDANCE VARIATIONS by NATURAL PROCESSEs

Chapitre 4

I +dI +

f 1 dI = dI +I 1 f 1 f

et

(R + d R )( I + d I ) + i Ri
ou

f 1 d I = u R d I + RI 1 f 1 f

u + f i f Variations dabondances isotopiques 1 f R 1 f Ri d I = I d R

u + fsimple in- and outflow as well as with asource and sink Fig. 4.8. Model representing awell-mixed reservoir with 1 f composition f f I affecting theisotopic of thereservoir. For instance, during an infinitesimal time period dI has escaped R = i Ri + R0 i Ri (4.35) from the(river) water into theair through evaporation and exchange with theambient vapour. u + f u + f I 0

ou

Chapitre 4 Chapitre 4

et et Fig.4.8 ou et ou

exemple, pendant une priode de temps infinitsimale, dI schappe de leau (de la u +f i f la valeur or le cas prcdent, de de leau restante tend vers linfini, ici la valeur de augmente trs rivire) vers via R lair Rlvaporation d I =f I d R et lchange 1 avec la vapeur ambiante. i ( ) R + d R ( I + d I ) + R d I = R d I + RI 1 f 1 f rgulirement. Le rsultat le plus important de comparaison des tendances pour 18 et 2 avec i i u + f 1 f 1 f f u R i duR Id R discut en Sect. 7.5. rapport 0 sera i laugmentation d I =I/I Integration and theboundary condition 1 f 1 f applying ou Lintgration et lapplication des conditions aux limites, i.e. R = R0 avec I = I0, conduit :

f 1 u + f Thestationary state I +dI + dI = requires d I + I that thesinks and I 1 f 1 1 balanced f for f theabundant sources are as well as i f i f (1 + i ) 1 (4.36) (4.36) f = 1 (1 + i ) + 1 + 0 I for therare isotope. is 4 mathematiI +d I+ dI = + I Chapitre u +This f d Icondition u + f 0 1 f by: 1 f cally presented Theresult of thelast model calculation is shown f 1 in Fig. 4.9 for and values as indicated in I +dI + dI = dI +I 1 du f dernier 1 f f est indiqu sur quindiques Le rsultat modle des valeurs de et telles thegraph. In thecase of flowing river water that 1 la Fig. 4.9 pour (dans )( I + d IDans R+d Rgraphe. ) + ile Ricas dune d I rivire = u R pouvant d I tre + RI le soumise lvaporation, la valeur de f dpend and is subjected to evaporation, thevalue of f depends 1 f 1 f Modle reprsentant un rservoir bien mlang avec un arbitrairement flux entrant et sortant simple, f le calcul 1 de lhumidit relative. Pour de la Fig. 4.9, f a t fixe 0,5. on therelative humidity. For thecalculation of ( R + d R )( I + d I ) + i Ri d I = u R d I + RI ainsi quavec une source 1 et isotopique du rservoir. Par une f fuite affectant 1 f la composition has arbitrarily 0.5. La diffrence avec lvaporation simple, uni-directionelle Fig.4.9, de la Fig.f4.4 est vidente: been tandischosen que, dans

R=R0 at I=I0 results in: u + f i f I = I d R u +R f i R f i 1 d f f R R1 i 1 f 1 f u + f I ln = ln f I0 u + f 1 i f Variations dabondances isotopiques 1 f R0 1 f Ri Variations dabondances isotopiques

(4.35) Fig. 4.9. Result of the model of Fig.4.8, represent(4.35)which evaporates continuing, for instance, a river ously during its course (Eq.4.36). Thevalue of f has ou been chosen 0.5. The and values can be realistic. or of et thecurve is almost astraight line, conou Fig.4.8 Modle reprsentant un rservoir bien mlang avec un Theshape flux entrant sortant simple, u + f 64 trary to thesimple evaporation ainsi quavec isotopique du rservoir. Par presented in Fig.4.4. et une fuite composition f une source i f affectant la I 1 f Asimilar curve can simple, be calculated for 2. Theratio be + f ( = ireprsentant 1+ i )+ 1 + ( 1 + ) 1 (4.36) Fig.4.8 Modle un rservoir bien mlang avec un flux entrant et sortant i 0 priode 1u f dI schappe exemple, pendant une de temps infinitsimale, de leau (de la + + f f I u f u f et une fuite tween thesedu two curves will I0 i i affectant la ainsi une composition Par be discussed in Sect.7.5. = quavec 1 + source (1 + i ) isotopique 1 ambiante. rservoir. (4.36) rivire) vers ( lair via lvaporation avec la vapeur i )+ 1 + 0 et lchange u + pendant f u + f infinitsimale, exemple, une priode de temps I 0 dI schappe de leau (de la rivire) lair via lvaporation lchange avec la vapeur ambiante. Fig.4.8 Modle reprsentant un bien avec un flux entrant et sortant simple,qui svapore Fig.4.9vers Rsultat durservoir modleet de la mlang Fig.4.8, reprsentant, par exemple, une rivire 41 ainsi quavec une source et une fuite affectant la isotopique du Par Lintgration et lapplication des conditions aux limites, i.e. Rcomposition =cours R0valeurs avec I= I0 , conduit : rservoir. et valeur telles quindiques Le rsultat du dernier modle est indiqu sur la au Fig. 4.9 de pour des de continuellement tout long son (Eq.4.36). La de f a t fixe 0.5. Les exemple, pendant une priode de temps infinitsimale, dI schappe de leau (de la dans le graphe. Dans le cas dune rivire pouvant tre soumise valeurs lvaporation, la valeur de f dpend valeurs de et sur semblent ralistes. La forme de la courbe estquindiques presque une ligne droite, et telles Le rsultat duet dernier modle est indiqu la Fig. 4.9 pour des de Lintgration lapplication des conditions aux limites, i.e. R = R avec I = I , conduit : 0 0 rivire) vers lair via lvaporation et lchange avec la vapeur ambiante. + f f de lhumidit relative. Pour le calcul de la Fig. 4.9, f a t arbitrairement fixe 0,5. contrairement au modle dvaporation simple prsent en Fig.4.4. Une courbe similaire u i dans le graphe. Dans le cas rivire pouvant tre soumise lvaporation, la valeur de f dpend R dune R

Finally, after some rearrangement: u + f I 1 f f f R = i Ri + R0 i Ri I 1u+f f u +f f u +f f 0 I Finalement, aprs quelques rarrangements: R = i Ri + R0 i Ri (4.35) u + f u + f I 0

INTRODUCTION

Thedifference between thesimple, one-directional evaporation of Fig.4.4 is obvious: while in theformer case theremaining of theremaining water approaches infinity, here the increase is

very regular. Theimportant result of comparing thetrends for 18 and 2 with increasing I/I0 will be discussed in Sect.7.5.

42

5. rADIOnuclide DECAY and production

This section contains abrief review of relevant facts about radioactivity, i.e. thephenomenon of nuclear decay, and about nuclear reactions, theproduction of nuclides. For full details thereader is referred to textbooks on nuclear physics and radiochemistry, and on theapplication of radioactivity in theearth sciences (cited in thelist of references). 5.1. Nuclear instability If anucleus contains too great an excess of neutrons or protons, it will sooner or later disintegrate to form astable nucleus. Thedifferent modes of radioactive decay will be discussed briefly. Thevarious changes that can take place in thenucleus are shown in Fig.5.1. In transforming into amore stable nucleus, theunstable nucleus looses potential energy, part of its binding energy. This energy Q is emitted as kinetic energy and is shared by theparticles formed according to thelaws of conservation of energy and momentum (see Sect.5.3). Theenergy released during nuclear decay can be calculated from themass budget of thedecay reaction, using theequivalence of mass and energy, discussed in Sect.2.4. Theatomic mass determinations have been made very accurately and precisely by mass spectrometric measurement: E = [Mparent Mdaughter] mc2 with 1 uma 931.5 MeV (5.2)) (5.1) 5.2. Nuclear decay and radiation In thenow following sections thevarious types of spontaneous nuclear disintegration will be discussed. 5.2.1. Negatron () decay

Themost abundant decay mode is - decay, involving theemission of anegative electron, a negatron or (beta) particle because of atransformation inside thenucleus of aneutron into aproton: n p+ + + + Q (5.3) This results in adaughter nucleus with equal Aand achange in atomic number Z to Z+1, and theemission of an electron and an anti-neutrino. A(anti)neutrino is aparticle with mainly arelativistic mass, i.e. mass because of its motion. (Neutrinos and negatrons have their spin antiparallel to their direction of motion and anti-neutrinos and positrons parallel). Thetotal reaction energy Q is shared between the particle and the(anti)neutrino. Theconsequence is that, although Q is aspecific amount of energy, theenergy spectrum of the particles is continuous from zero to acertain maximum energy at Emax=Q. Theenergy distribution is such that themaximum in this distribution is at an energy about one third of themaximum energy. As mentioned above, in some cases theresulting daughter nucleus is not in an excited state, so that no radiation is emitted. This happens to be thecase with thetwo isotopes that are relevant in isotope hydrology, viz. 3H and 14C. 5.2.2. Positron (+) decay

Disintegration of aparent nucleus produces adaughter nucleus which generally is in an excited state. After an extremely short time thedaughter nucleus looses theexcitation energy through the emittance of one or more (gamma) rays, electromagnetic radiation with avery short wavelength, similar to theemission of light (also electromagnetic radiation , but with alonger wavelength) by atoms which have been brought into an excited state. In some cases, however, decay is directly to theground state of thedaughter nucleus, without theemission of radiation. Fig.5.2 shows thevarious decay schemes of some familiar nuclides.

This type of nuclear transformation involves theemission of apositron or + (beta plus) particle as theresult of atransformation inside thenucleus of aproton into aneutron: p+ n + e+ + + Q (5.4)

and, because after slowing down thepositron reacts fast with an electron anywhere present:

INTRODUCTION

e+ + e 2

(5.5)

Here two electron masses are transformed into energy. Theprocess is called annihilation, theenergy released annihilation energy. With themass of theelectron me = 5.4858026104 (5.6)

theresulting energy is 1.022 MeV, which is represented by two oppositely directed g particles of 511 keV each. This type of decay is, for instance, known from naturally occurring 40K (Fig.5.2). 5.2.3. Electron capture (EC)
Fig. 5.1. Different modes of radioactive decay visualised on one spot of thechart of nuclides (cf. Fig.1.2). N is thenumber of neutrons, Z thenumber of protons.

Thenucleus may pick up one electron from theatomic electrons circling thenucleus in consecutive shells. In that case thefollowing reaction takes place: p+ + e n + + Q (5.7)

Depending on from which atomic shell theelectron is caught by thenucleus, electron capture is called K capture, L capture, and so on. + decay and EC leave themass number Aof thenucleus unchanged, while Z becomes Z1 (Fig. 5.1). Theatom is left in an excited state and returns

to theground state by emitting short-wave electromagnetic radiation, viz. low-energy g rays or X rays. As in theprevious decay modes, theexcited state of thenucleus causes theemission of one or more g rays.

Fig. 5.2. Decay schemes for some nuclides obeying -, + or EC decay, thelatter example of 40K in branching decay, and theconsecutive g radiation by theexcited daughter nucleus as well as theformation of 2g by annihilation of an emitted + particle.

44

rADIOnuclide DECAY and production

5.2.4.

Alpha () decay

(alpha) decay involves theemission of an particle (a4He nucleus):

A Z

A 4 Z2

Y +

4 2

He

Fig. 5.3. Aprs la dsintgration radioactive, le noyau fils M et la plus petite particu (5.8)

This type of decay occurs primarily within de dsintgration en tant qunergie cintique. theheavy elements such as in theuranium and Fig. 5.3. After radioactive decay thedaughter nucleus thorium series. Theemission of theheavy parM and thesmaller emitted particle m (for instance, an ticle practically coincides with theemission of particle) move opposite direction, together carryLe principe de conservation dein limpulsion ncessite: relatively large-energy g rays. ing thedecay energy as therespective kinetic energies.

exemple, une particule ) se dplacent en directions opposes, portant en

Because as in all cases thereaction energy Q MV + mv = 0 ou M2V2 = m2v2 is shared by theatoms Y and He according to thetwo conservation laws, thecase of emission tandis que le while principe deprinciple conservation de lnergie ncessite querelnergie de dsintg the of conservation of energy is special. As with agun shot, where therifleman la somme des deuxthedecay nergies cintiques: quires energy to be equal to thesum of feels alarge momentum against his shoulder, thetwo kinetic energies: thedaughter nucleus receives arelatively large Edsintgration = MV2 + mv2 = EM + Em so-called recoil. This is particularly important Edecay= MV2 + mv2 = EM + Em (5.10) where therecoil energy is large enough to loose A partir 5.9, nous avons: From Eq.5.9 we have: thedaughter nucleus from its chemical bond. Thisde lEq. phenomenon is thebasis for studying thenatural 1 1 1 m E M = MV 2 = M 2V 2 = m 2v 2 = E abundance of thedecay nuclides of uranium and Chapter 5 M m 2 2M Chapter 52M thorium. In Sect.5.3 we will deal with recoil en (5.11) Chapter 5 ergy quantitatively. Avec lEq. 5.10: m Eq.5.10: m With +decay = Edecay = 1E E Em m1 + M M m 5.2.5. Spontaneous and induced E dsintgra =m + 1 Em tion E EM = 1 + decay m fission, neutron emission M that theso two that particle the two energies particleare, energies respectively: are, respectively: Nuclides of theheavy elements so have thepossibilso that thetwo particle energies are, respectively: ity of breaking up into two relatively large daughso that the two particle energies are, respectively: m M m ter nuclei together with theemission of anumber M (5 =decay Em = Em E Edecay and and and EM = EM E Edecay =decay of neutrons. This decay may occur spontane+ + + M +m M M m m M m M m ously as well as induced by thebombardment Em = Edecay and EM = (5.12)Edecay M +m M +m of theparent nucleus by aneutron from else 238 U with aU decay with energy a decay ofenergy about 4.2 of about MeV,4.2 theMe da In the case In of thethe case of decay the of decay of 238 where, for instance from aneighbouring nucleus. 238 234 234In thecase of the238 U with adecay decay of nucleus, nucleus, Th, Th, a receives recoil energy a recoil ofU energy [4/(234+4)] of [4/(234+4)] 4.2 MeV of 4.2 =about 71 MeV keV, = mo 71 This is thedominant process in nuclear In reactors with a decay energy 4.2 Me the receives case energy of the decay of MeV, of about 4.2 thedaughter nucleus, (Sect.5.4.2; Chapter 12). 234break enough to enough break the to chemical the chemical bond between bond the between Th the[4/(234+4)] and Th atom the surrounding and surround atoms 234 nucleus, Th, receives a recoil energy of atom [4/(234+4)] 4.2 the MeV = 71 Th, receives arecoil energy of mineral (see mineral Sect.12.14 (see Sect.12.14 and Volume and 4 Volume on Groundwater) 4 on Groundwater) for a discussion for a discussion of the consequ of th 4.2 MeV = 71 keV, more than enough to enough to break the chemical bond between the Th atom and the surroundi break thechemical bond between theTh atom 5.3. Recoil by radioactive decay mineral (see Sect.12.14 and Volume 4 on Groundwater) for a discussion of the and thesurrounding atoms in themineral (see In thepreceding chapter we mentioned thephe5.4 5.4 NUCLEAR NUCLEAR REACTIONS Sect.12.14 and REACTIONS Volume 4 on Groundwater) for nomenon of therecoil momentum and eneradiscussion of theconsequences. 5.4 REACTIONS The overall The principle overallNUCLEAR of principle a nuclear of a reaction nuclear is reaction that a nucleus is that a isnucleus bombarded is bombarded by a particle by gy which any decaying nucleus experiences. However, in thecase of aheavy such as compound nucleus . This nucleus does . by Th no inparticle the first in instance the firsttaken instance up by taken the up nucleus by the tonucleus form a form a compound The overall principle of a nuclear reaction isto that a nucleus is bombarded 5.4. Nuclear reactions theparticle leaving thenucleus, theeffect is not in a stable inthe particle. a stable Within particle. anWithin extremely anthe extremely short time short the compound time the compound nucleus will nucleu lo nucleus . Thi in first instance taken up by nucleus to form a compound negligibly small. We will now calculate therecoil Theoverall principle of nuclear reaction is excess energy excess by the particle. release by the of release one oran of more one particles, ora more ultimately particles, ultimately forming aforming new nuclid an in a stable Within extremely short time the compound nucleu energy by considering theclassical mechanics ofenergy that anucleus is bombarded by aparticle that is bombarding bombarding particles may particles be "man-made" may be and originate and from originate a nuclear from a particle nuclear acce this process (Fig.5.3). excess energy the release of"man-made" one or more ultimately forming apa n in by the first instance taken up byparticles, the nucleus to (electrically (electrically charged particles) charged particles) or a nuclear or a reactor nuclear (highreactor or low-energy (highor low-energy neutrons), neu or form acompound . This and doesoriginate not resultfrom in a nuclear par bombarding particles may be nucleus "man-made" The principle of conservation of momentum refrom natural from origin. natural origin. astable particle. Within an extremely short time quires: (electrically charged particles) or a nuclear reactor (high- or low-energy neut thecompound nucleus will loose theexcess ennatural origin. examples A few examples may ergy serve may to therelease show serve the to convention show the convention of writing of nuclear writing reactions: nuclear reaction 2 from by of one or more particles, ulti= few m2v (5.9) MV + mv = 0 or M2V2A A few examples may serve to show the convention of writing nuclear reaction 36 36 36 36 Ar + n Ar p ++36 n Cl p + 36 or Cl or Ar(n,p)36 Cl Ar(n,p)36Cl 45 36 36 Ar + n p + 36Cl or Ar(n,p)36Cl
40 40 Ca + n Ca + +37 nAr + 37 orAr 40 40 40 or Ca(n.)37 Ar Ca(n.)37Ar 40

(5

Ca + n + Ar

37

or

Ca(n.) Ar

37

INTRODUCTION

mately forming anew nuclide. Thebombarding particles may be man-made and originate from anuclear particle accelerator (electrically charged particles) or anuclear reactor (high- or low-energy neutrons), or may be from natural origin. Afew examples may serve to show theconvention of writing nuclear reactions:
36 40 40

and He nuclei bombarding atmospheric nuclei (N, O, Ar); these reactions are theorigin of theatmospheric abundance of nuclides such as 3H, 7Be, 26Al, 32Si, 39 Ar and 85Kr; (b) low-energy reactions by thermal neutrons, of which theproduction of 14C in theair is thebest known example. These reactions will be discussed later together with thespecific treatment of thevarious isotopes (Chapters 8 and 12).

Ar + n p + 36Cl Ca + n + 37Ar Ar + n 2n + 39Ar

or or or

36 40 40

Ar(n,p)36Cl Ca(n.)37Ar Ar(n,2n)39Ar

(5.13) 5.4.1. Natural production

Nature is constantly and intensively performing nuclear reactions. Thebombarding particles originate from two sources: (1) From cosmic radiation, an avalanche of fragments of atmospheric nuclei, awide range of particles from photons and electrons to neutrons and mesons. These are primarily produced as secondary and tertiary particles in theupper atmosphere in aprocess called spallation, by very-high-energy cosmic protons and asmaller percentage of helium nuclei from thesun, from further away in our Galaxy and probably from extragalactic space. Mesons reaching theearth surface have avery high penetrating power and can be observed at great depth below theground or water surface. Variations in cosmic radiation occur because theorigin is to be found in events such as solar flares and supernova explosions. Also indirectly does thesun influence thecosmic ray flux in the atmosphere. The fact is that part of theincoming primary particles are deflected away from the earth by the earth magnetic field, which has not been entirely constant through geologic times. Thevariable magnetic field of the sun now adds to thevariations in theearth magnetic field and thus in theshielding capacity of theearth against cosmic particles. Cosmic radiation produces radioactive nuclei in theatmosphere primarily through two different types of reactions: (a) high-energy reactions by thesecondary particles such as protons, neutrons 46

(2) From nuclear decay particles, primarily neutrons from spontaneous decay of nuclides of theuranium, actinium and thorium decay series. These processes occur underground depending on theU or Th content of thesoil minerals (Chapter 12). 5.4.2. Anthropogenic releases of radionuclides

Also man has become able to produce nuclei and even elements, presently unknown in nature, on asmall scale in thelaboratory, but also on alarge scale in thenatural environment by thetest explosion of nuclear weapons. Theanthropogenic releases of radioactivity are related to these nuclear weapons testings as well as to theregular or incidental releases by nuclear (power) industries. Therelease of radioactivity related to thetesting of nuclear weapons has two main causes, viz.: (1) Fission bombs, based on theneutron-induced fission reaction of uranium or plutonium: U + n nucleus with A 85100+ nucleus with A 130145 + neutrons and likewise 239 Pu + n nucleus with A 95105 + nucleus with A 132142 + neutrons
235

Well-known examples of radioactive nuclides as products of theasymmetrical mass distribution of the long-living fission products are 93Zr and 99Tc on theone hand, and 129 I and 137Cs on theother. Industrial activities concerning nuclear power production and fuel reprocessing may bring on asmall scale nuclear waste materials in theenviron-

rADIOnuclide DECAY and production

ment, similar to those that are being produced by thebomb explosions. Aspecial case of nuclear waste release is theoccurrence of nuclear reactor incidents. In some cases (Chernobyl in 1986) sufficient radioactivity was injected into theenvironment to detect certain isotopes in nature, for instance in sediments and ice cores.

is sufficiently high to produce radioactive nuclides that are also being made by nature itself: C + 3H or 14N(n,3H)12C a n d 14 N + n 14C + 1H or 14N(n,p)14C
14 12

N + n

(2) During thenuclear explosions especially theneutron density in thesurrounding air

H (tritium) and 14C (radiocarbon), and other cosmogenically as well as anthropogenically produced isotopes will be discussed in detail in Chapter 8 and 12.
3

47

6. EQUATIONS OF RADIOACTIVE DECAY AND GROWTH

Themathematical expressions presented in this 1000 chapter are generally applicable to all those processes in which thetransition of theparent nucleA0 800 us to adaughter nucleus, i.e. theprocess of raT 1/2 2T 1/2 dioactive decay, is governed by statistical chance. 600 This chance of decay is equivalent to thedegree of instability of theparent nucleus. Each radioac1/2 A 0 400 tive nuclide has its specific degree of instability which, as we will see, is going to be expressed by 200 thehalf-life assigned to this dans nuclide. Les expressions mathmatiques prsentes ce chapitre sont gnralement applicables tous les

EQUATIONS DE DESINTEGRATION ET CROISSANCE RADIOACTIVE

A

1/4 A 0

processus dans lesquels la transition du noyau au noyau fils, i.e. le processus de dcroissance Theradioactivity of asample is pre more complicat0 radioactive, est gouvern par des chances statistiques. Cette est quivalente ed if it consists of two or more components,chance such de dsintgration 0 10 20 30 40 50 60 time in hours au degr dinstabilit noyau of pre. Chaque of nuclide radioactif a son degr spcifique dinstabilit as: (i) in du thecase amixture independent activities, (ii) if one specific type of nuclide shows qui, comme nous allons le voir, est exprim par la demi-vie associe ce nuclide.

70

80

90

100

two modes of decay, so-called branching decay, Fig. 6.1. The rate of radioactive decay. After each La radioactivit plus complique si il comporte ou plusieurs composants, and dun (iii) chantillon if we are est dealing with anuclear decay deux subsequent half-life of 20 hours the number of racoe: (i) dansseries le casin dun mlange dactivits indpendantes, type spcifique de nuclide which also thedaughter nuclides are(ii) ra- si un dioactive nuclei and theoriginal radioactivity of 800 montre deuxdioactive. modes de All dcroissance, appels dcroissance multidirectionnelle, et (iii) si nous nous these phenomena will be discussed units are divided into half. intressons separately. une srie de dsintgration radioactive dans laquelle les noyaux fils sont radioactifs. Tous ces phnomnes seront discuts sparment. and subsequently theequation of exponential deThefundamental law of radioactive decay is cay: La loi fondamentale dethefact dcroissance radioactive i.e. est base sur le fait que la dcroissance, i.e. la based on that thedecay, thetransition of aparent nucleus nucleus is transition dun noyau pre un noyau to filsadaughter est un processus purement statistique. (6.5) N = N0et La probabilit de apurely statistical process. Thedisintegration dsintgration (dcroissance) est une proprit fondamentale du noyau atomique et reste quivalente or using Eq.6.3: (decay) probability cette is afundamental property dans le temps. Mathmatiquement, loi sexprime ainsi: of an atomic nucleus and remains equal in time. (6.6) A = A0et Mathematically this law is expressed as:
6.1 LOI DE DCROISSANCE RADIOACTIVE dN = N dt et

6.1. Law of radioactive decay

ln(N/N0) = t (6.4)

dN = N dt (6.1) and

Thetime during which A0 decreased to A(=theage of thematerial) is: T = (1/)ln(A/A0)

(6.2)

(6.1)

Therelations of Eqs.6.5 and 6.6 indicate therate at which theoriginal number of radioactive nuclei where N is thenumber of radioactive nuclei, dN/ ou N est le nombre de noyaux radioactifs, -d N /d t la dcroissance (ngative) ce nombre par unit de and theoriginal radioactivity (A0) decrease (N 0)de dt thedecrease (negative) of this number per unit in time (Fig.6.1). probabilit dsintgration par noyau per et par unit de temps. Cette constante temps, et est of donc time la and is thusde theprobability of decay nucleus per unit of pour time. This decay constant is de chaque nuclide. de dsintgration est spcifique chaque mode de dsintgration specific for each decay mode of each nuclide. 6.2. Half-life and mean life
La radioactivit ou taux de dsintgration est dfinie comme le nombre de dsintgration par unit de The radioactivity or decay rate is defined as temps: It is acommon practice to use thehalf-life (T1/2)

( d N / d t )
N

(6.2)

(6.7)

thenumber of disintegrations per unit of time:

A = dN/dt = N

A = dN/dt = N (6.3)

By integration of this relation and applying theboundary conditions that at in thebeginning t=0 and N=N0 we obtain:

instead of thedecay constant () for indicating (6.3) or thedecay rate of arathedegree of instability dioactive nuclide. This is defined as the period of time in which half of theradioactivity has disappeared (half of thenuclei have disintegrated, Fig.6.1):
75

Celle ci demi-vie est dfinie comme laplace priode de temps bout duquel la moiti de la radioactivit a disparue (la moiti des nuclides sedutiliser sont dsintgrs, Fig.au 6.1): dutiliser la (T de constante de 1/2) la Il est de pratique courante la la demi-vie (T1/2 ) dcroissance la place de la constante de dcroissance INTRODUCTION (la moiti des nuclides se sont dsintgrs, Fig. 6.1): r le degr dinstabilit ou taux de dcroissance dun nuclide radioactif. radioactive () pour indiquer le degr dinstabilit ou taux de dcroissance dun nuclide radioactif. (1/duquel )ln(1/2) (6.8) T1/2 a priode de temps au = bout la moiti de la radioactivit a disparue Celle ci est dfinie comme la priode de temps au bout duquel la moiti de la radioactivit a disparue (6.8) T1/2 = (1/)ln(1/2) ont (la dsintgrs, Fig. 6.1): where: = (se 1/ )ln(1/2) (6.8) T1/2 moiti des nuclides sont dsintgrs, Fig. 6.1): A partir de quoi : =(ln2)/T1/2=(ln2)/12.43 a(1 year=3.16 107 s) from A partir de quoi : which: ) A(G/M=number of N=21018 (G/M 1/2) (6.8) (6.8) T1/2 = (1/)ln(1/2)

Il est de pratique courante dutiliser la demi-vie (T1/2) la place de la constante de dcroissance Il est de pratique courante dutiliser demi-vie (ou T1/2taux ) la de la constante de dcroissance radioactive () pour indiquer le degr la dinstabilit deplace dcroissance dun nuclide radioactif. VIE MOYENNE radioactive ( ) pourcomme indiquer degrde dinstabilit ou taux de dcroissance dun nuclide radioactif. 6.2 DEMI-VIE ET VIE MOYENNE Celle ci est dfinie la le priode temps au bout duquel la moiti de la radioactivit a disparue

(time): theyear AD 1950) (see 14C standard activity, t t 1 (in 1 t t = = + = 0 t N t t t d d e e d t e t 8): t la priode 0 Chapter 1 les 1 t t oyaux (N) donnepour la denoyaux demi-vie e N Lintgration )0 donne demi-vie 0 t 0e de +(temps): =tous priode (temps): N d t =(N t e d t = d t 0 0 0 14 C 13.56 5730(6.10) N 0 (3.16 10 7 ) 12 0 1 1 t 1 (6.10) = = 1.2 10 12 23 = = 0 + e t 1 C 0 60 ln 2 ( 6 . 02 10 ) 1 1 t 1 1 t 1 t t et t = + dt = t e d e et d = te = t = + e t 0 + e t d t dt d N tt= = 0 0 0 0 (6.12) N 0 0 0 0 (6.10) 0 (6.10) 14 1 la vie 1 A C avec T = 5730 ans est de 8267 ans. Ainsi = titre dexemple, moyenne dun noyau de 1 1 1 1/2 t e = = 0 + e t 0 = 14 0 dexemple, 6.4. Mixture of independent C avec T = 5730 ans est de 8267 ans. Ainsi = A titre la vie moyenne dun noyau de 1/2 1/8267, ce qui signifie que lactivit dun chantillon dcrot de 1 en environ 8 ans; lactivit dun (6.10) 3 radioactivities 1/8267, ce qui que lactivit dun chantillon dcrot depar 1 en environ 8 ans; lactivit dun chantillon de signifie H (T1/2 = 12,43 a), quant elle, diminue de 5,6% an. 3 an example, themean life of a14C nucleus with As chantillon de H ( T = 12,43 a), quant elle, diminue de 5,6% par an. 14 1/2 6.2 shows decay curve avec T1/2 = 5730 ans estde de14 8267 ans. Ainsi = ansFig. yenne dun noyau de laC C avec T1/2 = 5730 est de 8267 ans. asemi-logarithmic Ainsi = A titre dexemple, vie moyenne T1/2=5730 ais dun 8267noyau years. Then =1/8267, of amixture of two activities that are completely 6.3 dun ACTIVITE, ACTIVITE ET CONCENTRATION EN lactivit dun activit chantillon dcrot de 1 en SPECIFIQUE environ 8 ans; lactivit dun 1/8267, ce qui signifie lactivit dun chantillon dcrot de 1 en environ 8 ans; which que means that asample activity decreases 6.3 ACTIVITE CONCENTRATION EN acomposite decay curve. If thehalf3 RADIONUCLEIDES 43 a), quant elle, diminue chantillon de 3ACTIVITE, H (T1 12,43 a),par quant SPECIFIQUE elle, a diminue deET 5,6% par an. independent, by in 5,6% about 8an. years; H sample activity 1/2 = de life values are sufficiently apart, it is seen to be RADIONUCLEIDES (T1/2 =12.43 a) decreases by 5.6% year. Lactivit dun chantillon donn est le nombre de per dsintgrations radioactives secondethetwo pour cetseparate decay curves, possible par to unravel CTIVITE SPECIFIQUE ET CONCENTRATION EN L activit dun chantillon donn est le nombre de dsintgrations radioactives par seconde pour 6.3 ACTIVITE, ACTIVITE SPECIFIQUE ET CONCENTRATION EN chantillon dans son ensemble. Lactivit spcifique, dun autre ct, est dfinie comme le nombrecet de side of thecurve, starting at theright-hand 14 3 EIDES chantillon dans son ensemble. Lactivit spcifique , dun autre ct, est dfinie comme le nombre de RADIONUCLEIDES C et H, Chapitre 8). dsintgrations par unit de poids ou de volume dchantillon (voir act. spc. du 6.3. Activity, specific activity and where theone activity has already disappeared. 3 C et H, Chapitre par 8). dsintgrations par unit de poids ou de volume dchantillon (voir act. spc. du 14 radionuclide concentration Lunit de radioactivit est le Becquerel (Bq), qui est dfini comme le taux de dsintgration Subtracting thestraight donn est le nombre de dsintgrations par seconde pour cet Lactivit dun chantillon donn estradioactives le nombre de dsintgrations radioactives par seconde pour cet semi-logarithmic curve Lunit radioactivit Becquerel (Bq), qui est dfini comme le taux de dsintgration par seconde (dps) ou, activity aujourdhui obsolte, le Curie (Ci) qui taitct, dfini comme le taux de from thecomposite curve le.chantillon L activit de spcifique , dun est autre ct, est spcifique dfinie comme le nombre de The ofle acertain sample is thenumber of dans son ensemble. L activit , dun autre est dfinie comme ledsintgration nombre de gives thestraight line 10 ou, aujourdhui obsolte, le Curie seconde (dps) (Ci) qui tait dfini comme le taux de dsintgration 14 for theshorter-lived nuclide. dps. de 10 aradioactive disintegrations per forChapitre thesamCsec et 3H, 8). spc. poids ou3,7 de volume dchantillon (voir act. spc. du dsintgrations par unit de poids ou de volume dchantillon (voir act. du 14C et 3H, Chapitre 8). 10 dps. de 3,7 10 ple as est awhole. The specific activity , on theother le Lunit Becquerel (Bq), qui dfini comme taux despcifique dsintgration par dedexemple radioactivit est le Becquerel (Bq), qui est dfini comme le taux et de la dsintgration A titre de la relation entre le lactivit dun chantillon concentrationpar dun hand, is defined as thenumber of disintegrations 3 le taux ui obsolte, le Curie (Ci) qui tait dfini comme le taux de dsintgration 6.5. Branching decay seconde (dps) ou, aujourdhui obsolte, le Curie (Ci) qui tait dfini comme de dsintgration A titre dexemple de la relation entre lactivit spcifique dun chantillon et la concentration dun noyau radioactif, nousweight allons calculer lactivit spcifique tritium ( H) dune eau contenant un per unit or volume of sample (see en spec. 10 3 18 allons calculer lactivit spcifique en tritium (3H) dune eau contenant un radioactif, nous dps. denoyau 3,7 10 14 atomes 3dhydrogne (quivalent 1 UT = Unit Tritium cf. Chapitre 8): atome de H pour 10 Also in nature radioactive nuclides exist that act. of 18 C and H, Chapter 8). Theunit of radioatome de 3H pour 10 is atomes dhydrogne (quivalent is 1 UT = dun Unit Tritium cf. Chapitremodes 8): activity the Becquerel (Bq), which defined show two different of decay. One example tion entre lactivit spcifique dun chantillon et la concentration A titre dexemple de la relation entre lactivit spcifique dun chantillon et la concentration dun 77 40 3 as adecay rate of one disintegration per second 3 K that can is presented by eau contenant un ( H) dune eau contenant un77 decay with theemisns noyau calculer lactivit nous spcifique tritiumlactivit ( H) dune radioactif, allons en calculer spcifique en tritium (dps) or thenow obsolete Curie (Ci) which was sion of a- or a+ particle (Fig.5.1). s dhydrogne 1 UT = Unit Tritium cf. Chapitre 8): atome de 3H (quivalent pour 1018 atomes dhydrogne (quivalent 1 UT = Unit Tritium cf. Chapitre 8): defined as adecay rate of 3.71010 dps. its specific decay constant 77 Each decay mode has 77 As an example of therelation between thespecifor half-life. Thetotal decay is simply thesum of ic activity of asample and theactual concentraboth single chances and is thus given by: tion of theradioactive nuclide, we will calculate thespecific tritium (3H) activity of water contain(6.13) total = 1 + 2 ing one 3H atom per 1018 hydrogen atoms (equivand thetotal half-life consequently by: alent to 1 TU=Tritium Unit (Chapter 8):

dede noyaux Ils ont exist se pendant une priode t,exist ce qui tempsse dt,dsintgre. un nombre dN denoyaux dsintgre. Ils ont pendant une priode t, ce qui tdN = tNdt As another example we can calculate the14C e global, pour d N noyaux, de: correspond untd temps de vie N = tN dt global, pour dN noyaux, de: Lintgration pour tous les noyaux (N) donne la priode de demi-vie (temps): concentration in carbon, which has a specific 14 LintgrationIntegrating pour tous lesover noyaux ( N) donne la priode de demi-vie (temps): all nuclei ( N ) gives themean life C activity of 13.56 dpm per gram of carbon tdN = tNdt

moles) (6.9) A= Avogadros number=6.02 1023/mol (6.9) T1 / 2 T1 / 2 M=molecular weight=18.0 The mean life of anuclide is thesum of thelife 12 Curie=3.7 102 dps pCi=pico-Curie=10 la somme des temps de demi-vie dun nombre de noyaux donns 93 La vie moyenne lndun 2 of nuclide 0 ,693 est times acertain number of nuclei (before they = dun (6.9) donns = nuclide est la somme des temps de(6.9) =0.037 Bq La vie quils moyenne demi-vie dun nombre de noyaux (avant ne se all soient dsintgrs) divise le nombre desdits noyaux. Pendant lintervalle T1 T1 /tous have disintegrated) divided by par thenumber of 2 /2 2 (avant quils ne soient tous dsintgrs) divise par le nombre desdits noyaux. Pendant lintervalle Thenumerical result water with 1 TU of tride temps dt, nuclei. un se nombre d N de noyaux se dsintgre. Ils ont exist pendant une priode t, for ce qui During thetime interval dt anumber of de dt ,des un nombre dvie N de noyaux senombre dsintgre. Ils ont donns exist tium pendant is: une priode t, ce qui d N nuclei disintegrate. These lived during apecorrespond temps de global, pour d N noyaux, de: de La est latemps somme temps de demi-vie dun de noyaux vie moyenne dun nuclide est la somme des temps de demi-vie dun nombre de noyaux donns riod t , which amounts to atotal life time for d N correspond un temps de vie global, pour d N noyaux, de: us dsintgrs) par letous nombre desdits noyaux. Pendant lintervalle (avant quilsdivise ne se soient dsintgrs) divise par le nombre desdits noyaux. Pendant lintervalle Bq/L = 3.19 pCi/L (6.11) Aspec = 0.118 nuclei of (cf. Nd t Eq.6.3): t d N = t

= = ln 2 0,693 T 1 / 2 A partir de quoi := = T1 / 2

ln 2

0,693

(6.9)

Aspec = N (par litre) 50

(1/T1/2)total = (1/T1/2)1 + (1/T1/2)2

(6.14)

celle des sries de U et Th (Part.12.14-12.16).

Dans ce contexte, nous pouvons nous limiter un seul lment de cette chane multiple: la relationnous entre pouvons une activit pre et fils. relations dun de deuxime et plu Dans ce contexte, nous limiter Les un seul lment cette chane traites ailleurs (voir les livres de Friedlander et relations al. et de Faure). EQUATIONS OFt RADIOACTIVE DECAY AND GROWTH multiple: lapar relation entre une activit pre et fils. Les dun deuxime et plu

If aradioactive nuclide is situated in theChart of d N1 Nuclides far from thestability line (for thelight = 1 N 1 A1 = dd N t1 elements at Z=N), thedaughter nucleus after = 1 N 1 A1 = dt radioactive decay may be radioactive as well. decay In nature this occurs with theheavy nuclides in et theuranium and thorium decay series (Chapter et 12). Here theoriginal decay of 238U or 232Th is folN 1 = N 10 e 1t and A1 = A10 e 1t decay lowed by aseries of radioactive decay products. N Fig.6.3. Reprsentation schmatique dune hypothtique courbe de dcroissance analogue A10 e 1t N 1 = N 10 multiple, e 1t and A1 = Fig.6.3 shows schematically how theelements of Fig. 6.3. multiple, Schematic representation a hypothetical celle sries de Uare et Th (Part.12.14-12.16). La quantit de noyaux fils est fonction de processus: (i) la dcroissance radio Fig.6.3. Reprsentation schmatique dune hypothtique courbe de dcroissance analogue deux of suchdes decay series related.

t traitespre par ailleurs les livres Friedlander de Faure). radioactive tr Le noyau dcrot (voir en accord avecde les quations et deal. la et dcroissance partie: Le noyau pre dcrot en accord avec les quations de la dcroissance radioactive tr 6.6. Radioactive decay series partie: Z

multiple decay curve, analogous to thedecay curves of dcroissance radio radioactive par dcroissance des pres, respectivement: La quantit de noyaux fils est fonction denoyaux deux processus: (i) la celle des sries de U et Th (Part.12.14-12.16). croissance In this context we can restrict ourselves to one eltheU and Th decay series (Sect.12.1412.16). croissance radioactive par dcroissance des noyaux pres, respectivement: ementnous frompouvons themultiple therelation Dans ce contexte, nous decay limiter chain: un seul lment de d cette N 2 chane de dcroissance between aparent and adaughter activity. There= et + 1niveau N1 2 N 2haut multiple: la relationnous entre pouvons une activit pre et fils. relations dun deuxime plus on Dans ce contexte, nous limiter Les un seul lment cette N d t 2 chane de dcroissance lations in asecond and higher degree have been de d N N = + (6.17) t traites ailleurs (voir les livres de Friedlander et relations al. et de Faure). 2 2haut 1 1 multiple: lapar relation entre une activit pre et fils. Les dun deuxime et plus niveau on
t traitespre par les livres Friedlander de Faure).de etailleurs al. and(voir byaccord Faure). La solution cette quation diffrentielle est: Le noyau dcrot en avecde les quations et deal. la et dcroissance radioactive traites dans cette Thesolution of this differential equation is: partie: La solution de cette quation diffrentielle est: Le noyau pre dcrot en nucleus accord avec les quations de latheequadcroissance radioactive traites dans cette Theparent decays according to partie:

treated elsewhere (see textbooks by Friedlander

dt

et et

1 0 0 N2 = N 1 (e 1t e 2t ) + N 2 e 2t (6.18) tions of radioactive decay which we have treated 0 0 1t Dcroissance d N1 ) N 2 = 2 1 1 N 1 (eEquations e 2tde + N 2 e 2t Radioactive in this section: = 1 N 1 (6.15) A1 = 1 activity 0 2 zero while et at t1 = zero 0): time (N2 =0): tandis qu activit temps zro (N20at N dd A1 = = 1 N 1 (6.15) (6.15) tandis qu activit et temps zro 2 (N20 =0 0): dt A = N = A1 (e 1t e 2t ) (6.19) 2 2 2 80 Equations de Dcroissance Radioactive 2 1 and
N 1 = N 10 e 1t and A1 = A10 e 1t
80
Equations de Dcroissance Radioactive

Thelast term represents (6.16) thedecay of theamount (6.16) Le dernier terme reprsente la dcroissance des quantits noyaux fils prsents au te of daughter nuclide present at de thetime 2 that 0 1t 0 1t 0 was 1t 2 t N = N e and A = A e (6.16) A = N = A e e 1 1 1 1 et est le facteur principal qui dtermine lvolution vident que le rapport entre 2 0. 2 1 1 Theamount of daughter nuclei is determined by t = It 2is obvious that theratio between 1 2 12 (ii) 0 la La quantit de noyaux fils est fonction de deux processus: (i) la dcroissance radioactive 1t 2 t 2 et temps. allons rappeler les trois diffrents cas relat two processes: (i) radioactive decay anddans (ii) le raand 2 2 is determines ANous N 2thedominating =maintenant A1 brivement e factor e that 2 = croissance radioactive par dcroissance des pres, respectivement: 2 et 1 (ii) la activity in time. We La quantit de noyaux fils est fonction denoyaux deux processus: (i) la dcroissance radioactive thecourse ofthedaughter dioactive growth by decay of theparent nuclei, Le dernier terme reprsente la dcroissance des different quantits de noyaux shall now briefly mention the3 cases for fils prsents au te respectively: croissance radioactive par dcroissance des noyaux pres, respectivement: 6.6.1 EQUILIBRE SECULAIRE et est le facteur principal qui dtermine lvolution vident que le rapport entre this ratio. d N2 2 Le dernier terme reprsente la1 dcroissance des quantits de noyaux fils prsents au te = 2 N 2 + 1 N 1 (6.17) Ce type de relation entre activit pre et fils intervient quand la demi vie du noyau p dans le temps. Nous allons maintenant brivement rappeler les trois diffrents cas relat d t vident que le rapport entre 1 et 2 est le facteur principal qui dtermine lvolution d N2 (6.17) plus grande que celle du noyau fils. On peut citer les exemples des relations entre le 1000 = 2 N 2 + 1 N 1 dans le temps. Nous allons maintenant brivement rappeler les trois diffrents cas relat 6.6.1. Secular equilibrium dt 238 235 232 U, U et Th, et leurs produits de dcroissanc longue, de luranium et du thorium, La solution de cette quation diffrentielle est: 6.6.1 EQUILIBRE SECULAIRE This type of relation between parent and daugh12): La solution de cette quation diffrentielle est: 6.6.1 EQUILIBRE SECULAIRE ter activity occurs when of theparent Ce type de relation entre activit pre etthehalf-life fils intervient quand la demi vie du noyau p 1 0 0 N 100 N 1 e 1t e 2t + N 2 e 2t (6.18) 2 = << nuclide larger than that ofexemples thedaugh - relations 1 celle 2 is plus grande que duinfinitely noyau fils. On peut citer les des entre p le 2 Ce type de relation entre activit pre et fils intervient quand la demi vie du noyau 0 0 2 t 2 t 1 1 238 are 235 232 ter nuclide. Examples therelations between N2 = N 1 e 1t e + N e (6.18) 2 U,pre Uau et cours Th, et temps, leurs produits de dcroissanc longue, de luranium et du thorium, T 1/2 = 10 hrs LEq. 6.16 dcrit correctement lactivit vu que lEq. 6.19 sele t plus grande que celle du noyau fils. On peut citer les du exemples des relations entre 1 zro (N 0 = thelong-living isotopes of uranium and thorium, 0): tandis qu activit et2temps 2 238 235 232 12): U, U decay et Th, et leurs produits de dcroissanc longue, de luranium et du thorium, 238 232 U, 235U and Th, and their products (see 10 0 tandis qu activit et temps zro (N20 = 0): 1t 2 t 12): A = A1 12): e e Chapter 12<< 2 80 T 1/2 = 2 hrs 1 << << 22 LEq. 6.16 dcrit correctement lactivit pre au cours du temps, vu que lEq. 6.19 se t 80 ou pour 1 = 0, 1 Eq.6.16 properly describes in que lEq. 6.19 se t LEq.26.16 dcrit correctement lactivit pretheparent au cours duactivity temps, vu 0 10 0

( (

) )

ln A

( (

) )

time in hours

(6.20) Fig. 6.2. Semi-logarithmic plot of a composite decay = 0, ou pour 1 curve for a mixture of two independent radioactive dcrivant la or croissance for 1 = de 0, lactivit fille au cours du temps si nous prenons au d compounds with half-lives of 2 and 10 hours. ou Thelon pour 1 = 0, Fig. 6.4 montre lvolution des deux activits. Enfin, (pour t avec 2t ger-lived activity can be subtracted from thesum curve A2 = A10 1 e 2t (6.21) valeur de: (heavy line) to produce the semi-logarithmiclactivit straight fille atteint une 2 t 0 A2 = A1 1 e decay curve for theshorter-lived nuclide. dcrivant la croissance de lactivit fille au cours du temps si nous prenons au d A2 = A10 e 1t = A1 2t Fig. 6.4 montre lvolution des deuxfille activits. Enfin, avec dcrivant la croissance de lactivit au cours du (pour temps tsi nous prenons au d lactivit fille atteint une valeur de: 51 avec 2t Fig. 6.4 montre lvolution des deux activits. Enfin, (pour t en dautres termes, les activits mre et fille, deviennent quivalentes. lactivit fille atteint une valeur de: 1t de vie courte puisse augmenter dans un chantillon conten 0 fille Le fait quune Aactivit = A1 2 = A1 e vie longue 1t t utilis, par exemple dans les cas ou la mesure de la 0 a

0 1t Eq.6.19 time, whereas (e e A2 = A e 2t ) turns into: 1 2 t 0 ) A2 = A1 0(1 A2 = A1 (e 1t e 2t )

( (

) )

A =A e

=A

A2 = A1 e 1t e 2t
ou pour 1 = 0,

)
INTRODUCTION

(6.20)

A2 = A 1 e

0 1

2 t

(6.21)
1000
1/2

dcrivant la time croissance lactivit fille au cours du temps si nous prenons au dpart A2 = 0. La in thebeginning. Fig.6.4 if wede take A2=0 T = shows thecourses of both activities. (at avec 2t dans lEq. 6.20) Fig. 6.4 montre lvolution des deux activits. Enfin, Finally (pour t in Eq.6.20) thedaughter ac with 2t lactivit fillet atteint une valeur de:

describing thegrowth of thedaughter activity in

tivity reaches avalue of:

A2 = A10 e 1t = A1

ln A

T 1/2 = 0.8 hrs

(6.22)

100

(6.22)

en dautres termes, les activits mre et fille, deviennent quivalentes. Le fait quune activit fille de vie courte augmentercontaindans un chantillon contenant un noyau de 10 Thephenomenon that puisse in Equations de asample Dcroissance Radioactive 0 5 10 15 vie longue a t utilis, par exemple dans les cas ou la mesure de la radioactivit timedu in hours ing along-living nuclide ashort-living daughFig. 6.4. Relation between noyau fils est may plus facile celle du noyau pre. Ce in cas correspond la dtermination de the radioactivities of ter activity growque is applied, for instance Chapitre 6 a parent (straight line) and a daughter nuclide when cases where theradioactivity measurement ofdcrot dune demi vie de 140 ans, qui par lintermdiaire dune lactivit de 32Si Chapitre 6 the parent nuclide decays infinitely slow as com 32 theparthedaughter nuclide easier thanvers that of basseis nergie P dune demi vie de 14,3 jours et une dcroissance pared to thedaughter nuclide (half-lives of and 0.8 ent activity. Such case is theactivity determinaquerespectively), aprs avoiri.e. spar dcroissance haute nergie. LEq. 6.21 montre 32 hours, the case of secular equilibtion of Si with ahalf-life of about 140 years, chimiquement un 32Si pur, lactivit 32P augmente dans lchantillon unline taux tel que thesum of parent and rium. Theupper represents which decays through a low- energetic decay aprs demi vie fille, of lactivit fille sest leve 50% de sa valeur maximum A1: daughter activity. with ahalf-life 14.3 days and ahigh-ento 32Pune

in other words, parent and daughter activity become equal.

ergetic - decay. Eq.6.21 shows that after separating chemically apure 32Si activity 32P is growing into this sample at arate such that after one daughter half-life thedaughter activity has increased to 50% of its maximum value of A1: A2=1/2 A1 after one T1/2 A2=3/4 A1 after two T1/2 A3=7/8 A1 after three T1/2 , and so on.

1000
T 1/2 = 8 hrs

ln A

T 1/2 = 0.8 hrs

100

81

Fig. 6.5. Relation between the radioactivities of a parent and a daughter nuclide, when the half-life 6.6.2. Transient equilibrium of theparent is larger (but not infinitely) than that of Fig. 6.5. Relation entre les radioactivits dun nuclide parent et dun nuclide quand la demi-vie Fig.6.6 Relationfils, entre les radioactivits dun nuclide pre et dun nuclide fils thedaughter (half-lives of 8 and 0.8 hours, respectiveIn case, thehalf-life of theparent isde llment-fils du this parent est plus grande (mais pas infinie)nuclide que celle (demi-vie de 8 et Fig.6.6 Relation entre les radioactivits pre et dun nuclide de fils vie du est grande que dun cellenuclide de llment-pre (demi-vie ly): thefils case of plus transient equilibrium. The heavy line still larger than that of thedaughter nuclide but 0,8 heures, respectivement): cas de lquilibre transitoire. paisse montre la vieLa duligne fils est plus grande queand celle de ligne llment-pre (demi-vie respectivement) cas du non-quilibre. La droite est la fonction de sem shows thesum activity of parent daughter. not infinitely: somme des activits parents/fils. respectivement) cas du non-quilibre. La ligne droite est la fonction de lactivit de llment-pre. La courbe suprieure correspond sem la 1 < 2 de lactivit de llment-pre. La courbe suprieure correspond la mlange. 1 > 2 Growth of thedaughter after zero activity at zero mlange. La croissance de llment-fils aprs une activit nulle au temps zro Thedaughter se produit maintenant suivant activity is growing in thesample time now occurs according to Eq. 6.19. Astaaccording to Eq.6.19 (Fig.6.6). lquation 6.19. Un tat stationnaire est atteint aprs un temps pendant lequelsuffisamment lactivit de long, seule lactivit de llment-fils aprs un temps tionary state is reached after sufficient Finalement, time suffisant in llment-fils est plus importante que celle de llment pre, comme on peut sy attendre. Lafigure Finalement, aprs un temps suffisamment long, seule lactivit un taux plus lev: which thedaughter activity is larger than lactivit thepar- de llment-pre Finally, after disparat sufficiently long time, only daugh- de llment-fils 6.5 montre lvolution de chacune activits. lactivit disparat un taux plus lev:activity is ent activity, as is todes bedeux expected. Fig.6.5 shows de llment-pre ter activity will be left, since theparent

This consideration gives thetime required to gain sufficient daughter activity for aproper measurement after chemical separation of theparent and daughter nuclides.

10 0 5

time in hours

10

15

thecourse of both activities: 2 2 A2 = A10 e 1t = A1 2 1 2 1 6.6.3.

NON-EQUILIBRE

(6.23)

disappearing rate: 2 at0 ahigher A2 = A1 e 2t 2t A2 = 1 2 2 A10 e (6.23) 1 2

(6.24)

6.6.3

d A2 Here thehalf-life of thedaughter nuclide is larger =0 Ici, le temps de demi-vie de llment-fils est suprieur celui de llment-pre := d dA t2 = 0 than that of theparent: = dt 1 > 2

No-equilibrium

Aprs un priode de tmax lactivit dethedaughter llment-filsactivity atteindrareaches une valeur maximale pou After aperiod of tmax Aprs un priode de tmax lactivit de llment-fils atteindra une valeur maximale pou amaximum value for:

1 2 0 1tmax 2 A1 e A10 e 2tmax + 2 1t max t 0 2 1 2 2 1 A 0 e 2 max 1 A e + 2 1 1 2 1 2 1

ou Lactivit de 52 llment-fils crot dans lchantillon suivant lquation 6.19 (Fig. 6.6). ou

1 e t 1 e t

1 max 1 max

= 2 e 2tmax = 2 e 2tmax

Aprs un priode de tmax lactivit de llment-fils atteindra une valeur maximale pour: Aprs un priode de tmax lactivit de llment-fils atteindra une valeur maximale pour:

d A2 d A2 = 0 = dt = 0 = dt
ou ou

1 2 0 1tmax 2 2t max 1 2 A10 e 1tmax + 2 A10 0 e 2t max 2 A e A e + 1 1 1 1 2 2 EQUATIONS OF RADIOACTIVE DECAY AND GROWTH 2 1 2 1
1000

or 1t max 2t max e 1t max = 2 e 2t max 1 e = e 1 2 (6.25) thus reached at: 1 t max = 1 ln 2 t max = ln 2 1 2 1 2 1 1

(6.25) (6.25)
100

ln A

La valeur maximale pour lactivit de of llment-fils est alors atteinte Themaximum value thedaughter activity is : La valeur maximale pour lactivit de llment-fils est alors atteinte :

T 1/2 = 8 hrs

(6.26)

10

(6.26) (6.26)

T 1/2 = 0.8 hrs

84 84

Fig. 6.6. Relation between the radioactivities of aparent and adaughter nuclide, when thehalf-life of 6.7. Accumulation of stable the daughter exceeds that of the parent (half-lives of Equations de Dcroissance Radioactive daughter product 8 and 0.8 hours, respectively): thecase of no-equilibrium. Thestraight line is thesemi-logarithmic plot of Aspecial case of no-equilibrium as discussed theparent activity. Theupper Linsertion de lquation 6.25 dans lquation 6.19 montre quau moment o ce maximum est atteint,curve is thetotal activity in thepreceding paragraph occurs if thedaughter of themixture. les lments pre et fils sont quivalents (Fig. 6.6).

Inserting Eq. 6.25 in Eq. 6.19 shows that at thetime this maximum is reached, theparent and daughter activity are equal (Fig.6.6).

1 0 5

time in hours

10

15

product is not radioactive, in other words:

6.7

ACCUMULATION DE PRODUITS-FILS STABLES 2 = 0

(6.28) 3 in rock (Fig.6.2) and theaccumulation of He in 2 = 0 water during thedecay of 3H. We will take thelatThis dating method especially applied in 40 Ar lors de la dcroissance de 40K Ceci peut tre illustr paras deux exemples,to (i)calculate laccumulation de of ter process an example theage oceanography, but recently also in hydrology dans leau pendant la dcroissance de 3H. Nous dans les roches (Fig. 6.2) et (ii) laccumulationparent de 3He activity asample from theremaining and [29] makes avery strong appeal to theexamount daughter product. prendrons cetheaccumulated dernier processus commeof exemple pour calculer lgeperimental de lchantillon partir de (mass spectrometric) technique, as 3 lactivit rsiduelle de llment-pre et le taux daccumulation du produit-fils. theamount of He produced is extremely small. Starting from thegeneral relation of Eq.6.18 or This is shown here by an example of one litres of theabwe can simplyde correct for En partant de6.19 la relation gnrale lquation 6.18 ouand 6.19, nous pouvons simplement corriger pour 2=0 with apresent-day 3H activity of 100 TU sence ofdune an original quantity of de daughter (ahard(une water 2 = 0 et labsence quantit originelle llment-fils condition difficile pour which over aperiod of une 20 years has accumulatcondition for mthodes asuccessful application of thedat10 application avec succs des de datation mentionnes): ed of 5.110 mL STP (0C and 1033 hPa) of ing methods mentioned): 3 He. 1t 0 N 2 = N 1 (1 e ) (6.27) (6.27)
o la quantit de gaz accumule (V en litres STP) est relie au nombre datomes N2 par: 6.8

Un cas spcial de can "non-quilibre", comme discut dans le paragraphe prcdent, se produit si This be illustrated by two examples, (i) 40 llment-filstheaccumulation nest pas radioactif;of en40 dautres termes: Ar during thedecay of K

Theperiod of time elapsed since time zero (theage T) is:

where theamount of gas accumulated (V in litres STP) is related to thenumber of atoms N2 by:

Chapitre 6 6.8. Radioactive growth

N V= = N 22 2322 22 .4 L L reactions, because this phenomenon is, from V ,4 23 6 10 Pour complter cette tude, nous mentionnerons ici la production de radionuclid 6 10 amathematical point of view, very similar to que ce est, dun point de vue mathmatique, trs sim thecase of phnomne secular equilibrium as discussed in Since, instead of theoriginal 3H activity,nuclaires, theac- parce 3 dquilibre sculaire tel que discut en Part. 6.6.1, si le taux de production (P) e Sect.6.6.1, if theproduction aprs une priode de temps inconnue est rate (P) is constant. Puisque, lativity place after de lactivit originelle de H, theunknown period oflactivit time is known ractions peuvent prendre place un acclrateur de particle particules nuclaires ou d Thereactions may dans take place in anuclear measured), N10lEq. in Eq.6.27 be re-par connue (doit (to tre be mesure), N10 dans 6.27 doit has tre to remplac N 1, et subsquemment, N1 par accelerator or in anuclear reactor. Theproducnuclaire. Le taux de production du radionuclide est: placed bytelle N1, and N1 by theactivity lactivit (A1 = N1), de sortesubsequently que: tion rate of theradionuclide is: (A1 = N1), so that: dN A1 + T A1 T = P N 6 10 23 (6.29) T T T V = N 1 e (1 e ) = e (1 e ) = (ed t 1) 22,4 where N is thenumber of radioactive nuclei and is thedecay constant. Similar theso Eq.6.21, la constante de dsintgration. De f ou N est le nombre de noyaux radioactifs, et to La priode de temps coule depuis le temps zro (l ge T) est: for theactivity produced is: lEq. 6.21, la lution solution pour lactivit produite est:
T= ln 2,7 10 22 V + 1 A1 1

here theproduction of radionuclides by nuclear CROISSANCE RADIOACTIVE

For thesake of completeness we will mention

N = A = P(1 e t )

(6.28)

53

Cette mthode de datation spcialement applique enQuand ocanographie, mais plusde rcemment en le temps approche linfini, un tat stationnaire est atteint dans lequel la hydrologie (Schlosser et al., 1998) fait trs fortement appel aux techniques exprimentales dcroissance du radionuclide sont quivalentes. Ainsi, t = : (spectromtrie de masse), puisque la quantit de 3He produite est extrmement faible. Ceci est montr

dN = P N dt

(6.29)

ou N est le nombre de noyaux radioactifs, et la constante de dsintgration. De faon similaire INTRODUCTION lEq. 6.21, la solution pour lactivit produite est:

N = A = P(1 e t ) (6.30)
At time approaches infinity, astationary is being reached in which theradionuclide production and dcroissance decay du radionuclide quivalentes. are equal.sont Thus, at t=: Ainsi, t = :
= PP (6.31) A Amax max=

1000

A max = production rate 1/2 A max 3/4 A max

(6.30)

Quand le temps approche de linfini, un tat stationnaire est atteint dans lequel la production et la
Activity (Bq)
100
T 1/2 2T 1/2

10

(6.31)

Ceci est montr en Fig. 6.7, qui reprsente lvolution de la radioactivit dans le temps, de la mme of theradioactivity in time, comparably to 1 faon quen Fig. 6.4. Fig.6.4.
0 2 4

This is shown in Fig.6.7, representing thecourse

Le temps ncessaire produire certaines fractions de lactivit maximale atteignabletime est(hrs) Thetime pour required to produce certain fractions of maintenant: themaximum attainable activity is now: Fig. 6.7. Growth of radioactivity by a constant production rate P of 400 nuclides/sec, resulting in amaxiA = 1/2 = 1/2 Amax aprs une demi-vie A= 1/2PP =1/2 Amax after one half-life mum activity of 400 Bq. Thehalf-life of theproduced A= 3/4 P after aperiod of time=2T1/2 A = 3/4 P aprs une priode de temps = 2T 1/2 nuclide is 2 hours. A= 7/8 P after 3T1/2, and so on. A = 7/8 P aprs 3T1/2 , et ainsi de suite. themaximum This means that after 3 half-lives

10

activity de has practically been maximale reached. est pratiquement atteinte. Ceci signifie attainable quaprs 3 priodes demi-vie, lactivit

86

54

7. natural abundance of thestable isotopes of C, O and H

This chapter is concerned with thenatural concentrations of thestable isotopes of hydrogen, carbon and oxygen, with particular attention paid to those compounds relevant in thehydrological cycle. For each isotope separately, we discuss thenatural fractionation effects, internationally agreed definitions, standards, and reference materials, and variations in thenatural abundances. In order to help thereader to appreciate isotopic abundance values as they occur in nature, Fig.7.1 shows some actual isotope ratios and fractionations in achoice of equilibrium systems. Surveys of some practical data of all isotopes concerned are given in therespective Sections. 7.1. Table carbon isotopes 7.1.1. Thenatural abundance Thechemical element carbon has two stable isotopes, 12C and 13C. Their abundance is about 98.9% and 1.1%, so that the13C/12C ratio is about 0.011 [30]. As aresult of several fractionation processes, kinetic as well as equilibrium, theisotope ratio shows anatural variation of almost 100. Fig.7.2 presents abroad survey of natural abundances of various compounds, at thelow-13C end bacterial methane (marsh-gas), at thehigh end thebicarbonate fraction of groundwater under special conditions. In thecarbonic acid system variations up to 30 are normally observed. Wider variations occur in systems in which carbon oxidation or reduction reactions take place, such as theCO2 (carbonate) - CH4 (methane) or theCO2 - (CH2O)x (carbohydrate) systems. 7.1.2. Carbon isotope fractionations

It will later be shown that thepresence of dissolved inorganic carbon (DIC) in sea-, ground-, and surface water presents thepossibility of studying gas-water exchange processes and of measuring water transport rates in oceans and

R = 0.00014354 H 2O ( vapour)
2

R = 0.00198567 H 2O ( vapour) v/l = 78.4

18

18

v/l = 9.74

H 2O ( liquid) at 20 oC 2 R = 0.00015575 R = 0.0111421 CO 2 (gas)

13 13

H 2O ( liquid) at 20 oC 18 R = 0.00200520 R = 0.00200520 H 2O ( liquid) at 20 oC

18

g/b = 8.46

18

s/l = +30.42

o HCO 3 (bicarbonate) at 20 C 13 R = 0.0112372

18

CaCO 3 (solid calcite) R = 0.00206620

Fig. 7.1. Examples of isotope ratios of compounds in isotopic equilibrium and therespective isotope fractionations, as defined in Sect.3.3. As an example may serve the calculation of 13g/b as 13g/b 13g/b as 13g/b 1 with 13g/bb=0.0111421/0.0112372 =0.99154.

INTRODUCTION

TABLE 6.1. Thestable and radioactive isotopes of carbon: practical data for thenatural abundance, properties, analytical techniques and standards. Further details are given in Sect.7.1 and 8.1, and in Chapters 10 and 11.
12

13

14

stability natural abundance natural specific activity decay mode / daughter half-life (T1/2) decay constant (l) max. b energy abundance range in hydrological cycle reported as in instrument analytical medium usual standard deviation international standard with absolute value

stable 0.989

stable 0.011

radioactive < 1012 < 0.25 Bq/gC / 14N 5730 a 1,2110 /a= 1/8267 a1
4

156 keV 30
13

0 to 1012
14

or 13C SM CO2 0.03 VPDB

A, 14a, 14, or 14

dpm/gC, Bq/gC, %, or CPG, SSL, SMA CO2, C2H2, CH4, C6H6, graphite 1 to 1% at natural level Oxalic acid: Ox1, Ox2 13.56 dpm/gC

0.0112372

Note: MS=mass spectrometry, PGC=proportional gas counting, LSS=liquid scintillation spectrometry, AMS=accelerator mass spectrometry

in theground. In connection with studying these phenomena, thestable and radioactive isotopes of carbon and their interactions pay an important contribution, often together with thewater chemistry. In nature equilibrium carbon isotope effects occur specifically between the phases CO2-H2OH2CO3-CaCO3. Values for thefractionations involved only depend on temperature and are obtained from laboratory experiments. Asurvey is presented in Fig.7.3 and Table7.2. Thekinetic fractionation of specific interest is that during carbon dioxide assimilation, i.e. theCO2 uptake by plants. Therelatively large fractionation (up to about 18) is comparable to theeffect observed during absorption of CO2 by an alkaline solution. Aquantitative estimate shows that theisotope effect as aresult of diffusion of CO2 through air can not explain thefractionation (Sect.3.5). Theresulting value of 13 is 0.9956, 56

so that only 4.4 of thetotal assimilation fractionation in favour of 12C can be explained by thediffusion. Theremaining 13.6, therefore, has to be found in thesurface of theliquid phase and in thesubsequent biochemical process. Another kinetic process occurring in thesoil is thebacterial decomposition of organic matter to form methane (CH4). Here thelargest fractionation amounts to about 55. In this process CO2 is simultaneously produced with afractionation of +25, resulting in a13 value of about 0. Aspecial problem is thekinetic fractionation during uptake and release of CO2 by seawater. This fractionation is included in calculations on global 13 C modelling. First we have to emphasise that thedifference in isotopic composition between, for instance, gaseous CO2 and thedissolved inorganic carbon content of water can not be addressed by isotope fractionation between CO2 and DIC.

natural abundance of thestable isotopes of C, O and H

atmospheric CO2
marine HCO 3 marine carbonate marine plants marine plankton land plants C4 type land plants C3 type

groundwater HCO 3 fresh-water carbonate wood peat coal oil natural gas bacterial CH4 animal bone diamond

80

60

40
13

20

+20

VPDB ()

Fig. 7.2. General view of C/ C variations in natural compounds. Theranges are indicative for thematerials shown.
13 12

Table 7.2. Thechemical fractions are quantitaIsotope fractionation is thephenomenon that, due tively treated in Chapter 9. to an isotope exchange process, adifference between theisotopic composition of two compounds Originally 13k values for theuptake of CO2 by occurs, while seawater carbon consists of 3 fracseawater of about 15 were assumed, based tions, i.e. dissolved CO2 (H2CO3 is hardly preson experimental results of CO2 absorption by an ent), dissolved HCO! andd dissolved CO$. All alkaline solution [36]. However, [37] have reathese fractions are fractionated isotopically with Isotopes Stables de lHydrogne, de lOxygne et du Carbone 13 respect to each other. The R value of DIC is:
4
13 13 2 13 13

Isotopes de lHydrogne, de lOxygne et du Carbone s de lHydrogne, de lOxygne et 2du ou, en terme de fractionnements [CO aqCarbone ] Stables RCO respectifs: + [HCO 3 ] RHCO + [CO 3 ] RCO
()

+ c 13 c / b

13

Rb 13 RDIC =

ou en terme or dein valeurs : values: terms of

a 13 a / b + b + c 13 c / b 13 Rb (7.7) CT

fractionation

[CO 2 aq ] + [HCO ] + [CO ] 13 13 a b c + + 13 13 / / a b c b ou, en terme de fractionnements respectifs: spectifs: RDIC Rb = CT or in terms of therespective fractionations:

RDIC =

2aq

2 3

CaCO 3

s/b HCO 3 c/b

2 CO 3

(7.7) (7.7)

13

(7.7)

-4

CO 2

g/b a/b CO2 aq

-8
13

DIC = : ou en terme de valeurs

13

a 13 a / b + b + c 13 c / b CT

b +

a 13 a / b + c 13 c / b CT
-12

(7.8)
40

13 13 10 20 30 a 13 +cb a 13 a / b + c 13 c0/ b + c 13 c / b 13 13 a 13 a +c a/b / b + c c / b 13 quations dans lesquelles les parenthses indiquent les concentrations respectives, (7.8) qui sont t ( C) = /b + + DIC b (7.8) temperature b (7.8) CT CT C aussi identifies par unT a (acide), b (bicarbonate), et c (ions carbonate), ainsi tels que

a+b + c =dans C Les valeursles sont donnes dans Tableau 7.2. Les fractions chimiques sont of gaseous CO (g), quations lesquelles parenthses indiquent les concentrations respectives, qui isotopes enthses indiquent concentrations respectives, quilesont T.les where thebrackets indicate therespective confractionation for carbon 2 centrations, also denoted a(acid), quantitativement traites dans leare Chapitre 9. telsby CO2 ainsi (a), dissolved identifies par unwhich a carbonate), (acide), b (bicarbonate), et c (ionsdissolved carbonate), tels quecarbonate ions (c), and e), b aussi (bicarbonate), et c (ions ainsi que bTableau (bicarbonate), and donnes c (carbonate ions), so solid carbonate (s) with respect 13 a + bdans +c= valeurs sont dans lesont Tableau 7.2. Les fractions chimiques sont to dissolved HCO3 (b). donnes leC 7.2. Les fractions chimiques T. Les Originellement, les valeurs de lors du prlvement de CO par leau de mer sont estimes k 2 that a+b+c=CT. Thevalues are given in Theactual data and equations are given in Table7.2. quantitativement traites dans le Chapitre 9. hapitre 9. environ 15, sur la base des rsultats exprimentaux dabsorption du CO2 par une 13 alcalinede (Baertschi, 1952). Toutefois, Siegenthaler & (1981) ont dmontr Originellement, les valeurs kde lors dusont prlvement de CO par leau de mer sont estimes lors solution du prlvement CO leau mer estimes 2 Mnnich 2 par de 57 que cet exprimentaux effet ne sapplique pas des laction de leau de mer. Les calculs effectus par environ 15, sur dabsorption la base rsultats dabsorption du CO es rsultats du dissolvante CO2 exprimentaux par une 2 par une ces auteurs, ainsi (Baertschi, que& par Inoue & Sugimura (1985) et Wanninkhof (1985) ont montr que le solution alcaline 1952). Toutefois, Siegenthaler & Mnnich (1981) ont dmontr ). Toutefois, Siegenthaler Mnnich (1981) ont dmontr fractionnement pendant le prlvement de par CO est de mer. Les calculs effectus par que cet effet ne sapplique pasLes laction dissolvante de 2 leau action dissolvante decintique leau de mer. calculs effectus

Fig. 7.3. Temperature-dependent equilibrium isotope

INTRODUCTION

TABLE 6.2. TCarbon isotope fractionation in theequilibrium system CO2 HCO3CO3CaCO3.

t (C) 0 5 10 15 20 25 30 35 40
13

g/b a ()

13

a/g b ()

13

a/b c ()

13

c/b d ()

13

s/b e ()

13

s/g f ()

10.83 10.20 9.60 9.02 8.46 7.92 7.39 6.88 6.39

1.18 1.16 1.13 1.11 1.09 1.06 1.04 1.02 1.00

12.00 11.35 10.72 10.12 9.54 8.97 8.42 7.90 7.39

0.65 0.60 0.54 0.49 0.44 0.39 0.34 0.29 0.25

0.39 0.11 +0.15 + 0.41 +0.66 +0.91 +1.14 +1.37 +1.59

+10.55 +10.19 +9.85 +9.52 +9.20 +8.86 +8.60 +8.31 +8.03

Note: 13y/x represents thefractionation of compound y relative to compound x. Values for intermediate temperatures may be calculated by linear interpolation (see also Fig.7.3). T=t (C) + 273.15 K
a b c

g=CO2gaseous, a= dissolved CO2, b=dissolved HCO!, c=dissolved CO$, s=solid calcite. [31]:
13 13 13 13

g/b=9483/T + 23.89 a/g=373/T + 0.19 a/b=9866/T + 24.12 c/b=867/T + 2.52

(7.1) (7.2) (7.3) (7.4) (7.5) (7.6)

[19]:

From aand b: [32]:

d e

Our evaluation of the original data from [33, 34]: 13 s/b=4232/T + 15.10
13

From aand e):

s/g=+5380/T 9.15

soned that this effect does not apply to thedissolving action of seawater. Calculations by these authors as well as by [38] and [39] have shown thekinetic fractionation during CO2 uptake to be k (air sea)= 13k (atm.CO2 to CO2 taken up)=2.0 0.2
13

thechemical composition of seawater, which adds to theoverall temperature dependence. At 20C therespective relative concentrations in seawater at pH=8.20 are: CO2(aq)/CT=0.006, HCO!/CT=0.893 and CO$/CT=0.102 where CT is thetotal inorganic carbon concentration. By incorporation of theCO2 + OH- reaction (0.9995), theresulting 13 value is 10.1 to 10.6, depending on whether thehydration of CO2 to H2O is to be included. According to [38] thevalue is about 10, so that we can conclude to afractionation of released CO2 with respect to DIC of: k (sea air)= 13k (DIC rel. to CO2 released)=10.3 0.3
13

This value was confirmed by experiments of thelast author (2.4 0.8).(We have to remind thereader that these 13k values as well as those below are for kinetic fractionations and do not refer to Table7.2). Thekinetic fractionation during CO2 release by theocean reported by [37] needs acorrection [35]. By application of themost recent equilibrium fractionations of Table7.2 theequilibrium fractionation (13a/DIC) for dissolved CO2 with respect to total dissolved carbon at 20C is 0.99055. This fractionation factor is also determined by 58

Figure7.4 represents areview of equilibrium and kinetic fractionations relative to gaseous CO2 (left-hand scale) and theactual 13 values based

natural abundance of thestable isotopes of C, O and H

pH=8.2

+10

equilibrium
HCO 3

20 C CO2 3

kinetic

() rel. to air CO 2

+8 +6 +4 +2 0

oceanic DIC

+2 0

2
13 13

b/g

13

c/g

13

/g

13

VPDB ()

(seaair)

4 6 8 10

CO 2 CO2 (aq)
13

13

(air sea)
CO 2

atmospheric CO 2

13

2 4

a-g
taken up released by the sea

12

Fig. 7.4. Fractionation for theisotopic equilibrium between CO2(gas)-dissolved CO2(aq)-dissolved bicarbonate 13 (HCO values with 3 ) dissolved carbonate (CO$) [35]. Theright-hand scale indicates approximate natural respect to VPDB. Theright-hand part shows kinetic fractionations during uptake and release of atmospheric oceanic CO2, respectively. DIC is thetotal dissolved inorganic carbon content (CT).

on 13 (atm.CO2)=7.0 (right-hand scale). It is obvious that theisotopic compositions of CO2 released and taken up by theocean are equal, as is required by thecondition of stationary state of isotopic equilibrium between ocean and atmosphere. 7.1.3. Reporting 13C variations and the13C standard

storage, and has been replaced by another limestone, NBS19, of which the13 value has been compared by anumber of laboratories with theprevious standard. Based on this comparison an IAEA panel in 1983 [41] adopted this new standard to define thenew VPDB (Vienna PDB) scale as:
13

NBS19 / VPDB = +1.95

(7.9)

As described in Sect. 4.1, isotopic composi13 tions expressed as values are related to those of specific reference materials. By international agreement PDB was used as theprimary carbon reference (standard) material. PDB (Pee Dee Belemnite) was thecarbonate from acertain (marine) belemnite found in theCretaceous Pee Dee formation of North America. This material was theoriginal standard sample used in theearly days in Chicago and at CalTech, but has long been exhausted. TheUS National Bureau of Standards therefore distributed another (marine) limestone of which 13 had been accurately established in relation to PDB. This first standard available to thecommunity, Solenhofen limestone NBS20, was analysed by [40] and consecutively defined as:
13

Theabsolute 13C/12C ratio of PDB was originally reported as 0.0112372 [40], whereas aslightly different value of 0.011183 (0.1) was reported by [42]. Thedistinction between PDB and VPDB has been made for formal reasons, but thedifference is negligibly small (< 0.01). Henceforth all 13 values are reported relative to VPDB, unless stated otherwise. More details on measurement and calculation procedures are given in Chapter 11. Asurvey of other reference samples is given in Table11.2. 7.1.4. Survey of natural 13C variations

NBS20 / PDB = 1.06

In this way thePDB scale was indirectly established. Meanwhile NBS20 is considered to be no longer reliable, probably because of improper

In theother volumes certain aspects of natural 13 variations will be discussed in more detail. Here we will restrict ourselves to ageneral survey, particularly with regard to thehydrological cycle (Fig.7.5). 59

INTRODUCTION

7.1.4.1. Atmospheric CO2 Theleast depleted atmospheric CO2 had originally 13 values near 7. Since the19th century this value has undergone relatively large changes. In general, high values are observed in oceanic air far removed from continental influences and occurs in combination with minimal CO2 concentrations. More negative 13 values are found in continental air and are due to an admixture of CO2 of biospheric and anthropogenic origin (13 25), in part from thedecay of plant material, in part from thecombustion of fossil fuels [43, 44]. 7.1.4.2. Seawater and marine carbonate Atmospheric CO2 appears to be nearly in isotopic equilibrium with theoceanic dissolved bicarbonate. The 13(HCO!) values in theocean are about +1 to +1.5, in agreement with theequilibrium fractionation g/b at temperatures between 15 and 20C (Table7.2). According to thefractionation s/b we should expect calcite slowly precipitating in equilibrium with oceanic bicarbonate to have 13 values of +2.0 to +2.5. This is indeed thenormal range found for recent marine carbonates. [45] observed this isotopic equilibrium between marine to brackish-water shells and dissolved bicarbonate in thewater. 7.1.4.3. Vegetation and soil CO2 Plant carbon has alower 13C content than theatmospheric CO2 from which it was formed. Thefractionation which occurs during CO2 uptake and photosynthesis depends on thetype of plant and theclimatic and ecological conditions. Thedominant modes of photosynthesis give rise to strongly differing degrees of fractionation [46, 47]. TheHatch-Slack photosynthetic pathway (C4) results in 13 figures of 10 to 15 and is primarily represented by certain grains and desert grasses (sugar reed, corn). In temperate climates most plants employ theCalvin mechanism (C3), producing 13 values in therange of 26 3. Athird type of metabolism, theCrassulacean Acid Metabolism (CAM) produces alarge spread of 13 values around 17 [48]. TheCO2 content of thesoil atmosphere can be orders of magnitude larger than that of thefree atmosphere. Theadditional CO2 is formed in thesoil by decay of plant remains and by root respiration and consequently has 13 values centring 60

around 25 in temperate climates where Calvin plants dominate. 7.1.4.4. Fossil fuel As complicated biogeochemical processes are involved in thedegradation of terrestrial and marine plant material ultimately into coal, oil, and natural gas, therange of 13 values of these fossil fuels is larger, extending to more negative values, especially of biogenic methane (Fig. 7.5). Theglobal average of CO2 from thecombustion of these fuels is estimated to be about 27. 7.1.4.5. Global carbon cycle Biospheric carbon has a direct influence on 13 of atmospheric CO2. Thelarge uptake of CO2 by theglobal biosphere during summer and theequal release of CO2 during winter causes aseasonal variation in theatmospheric CO2 concentration as well as in 13. Thesimple mixing of CO2 from these two components, atmospheric CO2 (atm) and biospheric CO2 (bio) is represented by theequation (cf. Eqs.4.13 and 4.15): (13atm + 13)(Catm + Cbio)= 13atmCatm + 13bioCbio

(7.10)

where C stands for theCO2 concentration, DC for thebiospheric addition, and D13 for thevariation in the value. Numerically this comes to aperiodic (seasonal) variation of 13 bio 13 atm 25 + 7.85 13 = = 0.05 0 00 C bio C atm + C bio 353 per ppm of CO2 (7.11) Superimposed on this phenomenon is thegradual increase in theconcentration and theaccompanying decrease in 13 by theemission of fossil-fuel CO2. Thetrends are shown in Fig.7.6 and can be approximated by: 13 / CO2 = 0.015 / ppmor13 = 0.025 /year
13

(7.12)

at aCO2 concentration of 353 ppm and =7.85 over theNorthern Hemisphere, valid for 01/01/1990. Thesmaller /ppm value of Eq.7.12 compared to Eq.7.11 shows that thelong-term trend is not due to simple addition and mixing of additional

natural abundance of thestable isotopes of C, O and H

+5

marine bicarbonate calcite

freshwater bicarbonate calcite

0
exchange with atmosphere

atmospheric CO 2 roundwater HCO 3

25C

10

be caused by isotope exchange with atmospheric CO2 (13 7.5), ultimately resulting in values of 13 + 13b/g=7.5 + 9=+1.5, identical to oceanic values. Consequently, freshwater carbonate minerals may have marine 13 values. In these cases themarine character of thecarbonate is to be determined by 18 (Sect.7.3). In addition to HCO!, natural waters contain variable concentrations of CO2 with theeffect that the 13 value of DIC is lower than that of thebicarbonate fraction alone: in groundwater [18]), and in stream and river waters derived from groundwater (Fig. 7.8) the13(DIC) values are generally in therange of 12 to 15. 7.2. Stable oxygen isotopes

VPDB ()

5C

15

exchange with soil CO 2 C 4 plants

13

20
soil CO 2

25

30

C 3 plants coal oil

35
natural gas (CH 4)

7.2.1.

Thenatural abundance

40

Fig. 7.5. Schematic survey of 13 variations in nature, especially of compounds relevant in the hydrological cycle.

CO2 in theatmosphere. Thelarge oceanic DIC reservoir is levelling out thepurely atmospheric mixing effect through isotope exchange. 7.1.4.6. Groundwater and riverwater Soil CO2 is important in establishing thedissolved inorganic carbon content of groundwater. After dissolution of this CO2 theinfiltrating rain water is able to dissolve thesoil limestone: CO2 + H2O + CaCO3 Ca + 2HCO!
2+

Thechemical element oxygen has three stable isotopes, 16O, 17O and 18O, with abundances of 99.76, 0.035 and 0.2%, respectively [30]. Observation of 17O concentrations provides little information on thehydrological cycle in thestrict sense above that which can be gained from themore abundant and, consequently, more accurately measurable 18O variations (Sect. 3.7). We shall, therefore, focus our attention here on the18O/16O ratio ( 0.0020).
CO 2 concentration (ppm)
360 355 350 345 340 335 330 1978
-7.4
South Pole Mauna Loa

(7.13)

VPDB ()

(Fig.7.7). Because limestone generally is of marine origin (13 +1), this process results in 13 of thedissolved bicarbonate of about 11 to 12 (in temperate climates). In thesoil theHCO! first formed exchanges with theoften present excess of gaseous CO2, ultimately resulting in 13(HCO!)=13(soil CO2) + 13b/g 25 + 9=16 (Fig.7.5). Consequently, 13(HCO!) values significantly outside therange of 11 to 12 are observed in soil water as well as in fresh surface water such as rivers and lakes. In surface waters such as lakes 13 C enrichment of dissolved inorganic carbon can

1980

1982

1984

1986

1988

1990

1992

1994

1996

-7.5 -7.6 -7.7 -7.8 -7.9

Mauna Loa Hawaii South

Fig. 7.6. Trends of theconcentration and 13 of atmospheric CO2 of air samples collected by C.D.Keeling on top of the Mauna Loa volcano at the Island of Hawaii and at the South Pole. The seasonal variations have been removed from theoriginal data [49]. Thedates refer to 1 January of each year.

13

61

INTRODUCTION

Values of 18 show natural variations within arange of almost 100 (Fig.7.9). 18O is often enriched in (saline) lakes subjected to ahigh degree of evaporation, while high-altitude and coldclimate precipitation, especially in theAntarctic, is low in 18O. Generally in thehydrological cycle in temperate climates we are confronted with arange of 18 not exceeding 30. 7.2.2. Oxygen isotope fractionations

duced from 18O measurements on carbonate laid down by marine shell animals at known temperatures and water isotopic compositions. These data lost theoriginal interpretation of thetemperature dependence of thes/l by thelater realisation that themajor oceanic palaeotemperature effect is thechange in 18 of seawater and, consequently of carbonate formed in this water by theformation viz. melting of enormous ice caps on thepoles during or after ice ages. Kinetic effects are observed during theevaporation of ocean water, as oceanic vapour is isotopically lighter than would result from equilibrium fractionation alone. Thenatural isotope effect for oxygen ( 12) is smaller than could be brought about by fractionation by diffusion. Laboratory measurements resulted in 18d=27.3 0.7 [57] and 18d=27.2 0.5 (unpubl.). These experimental values are again smaller than results from Eq. (3.35) (31.3), which may be explained by thewater molecules forming clusters of larger mass in thevapour phase. Furthermore, evaporation of ocean water includes sea spray by which water droplets evaporate completely without fractionation, thus reducing thenatural isotope effect.

Theisotope effects to be discussed are within thesystem H2O (vapour) - H2O (liquid) - CaCO3. Theequilibrium fractionation values have been determined by laboratory experiments. Fig. 7.1 shows some actual isotope ratios. Fig.7.10 and Table7.4 present asurvey of thetemperature dependent equilibrium isotope effects. Equilibrium fractionations determined in thelaboratory are also found in nature. Themost striking observation is that thecarbonate shells of many molluscs appear to have been formed in isotopic equilibrium with seawater. Thepalaeotemperature scale as presented by Eq.7.18 was presented by [55] (cf. [53]). This relation is deatmosph.CO 2 7.5

exchange

precipitation

plants / humus 25
oceanic HCO 3 + 1

soil H 2O

humus CO2 25 marine CaCO 3 + 1

dissolved CO 2 25 1 soil CaCO 3 + 1 1

groundwater HCO 3 12 1

erosion / sedimentation

groundwater DIC 11 to 16

Fig. 7.7. Schematic representation of theformation of dissolved inorganic carbon in groundwater from soil carbonate and soil CO2. This is themain process responsible for thecarbonate content of groundwater and theconsecutive components of thewater cycle. Generally, dissolved bicarbonate is by far thelargest component. The values referring to therespective 13 have been kept simple for thesake of clarity. DIC is thedissolved inorganic carbon content of thewater, i.e. HCO!, CO2(aq) and CO$.

62

natural abundance of thestable isotopes of C, O and H

7.2.3.

Reporting 18O variations and the18O standards

-6 -8

13

(HCO 3 ) ()
Rhine

Originally 18O/16O of an arbitrary water sample was (indirectly, via alocal laboratory reference sample) compared to that of average seawater. This Standard Mean Ocean Water in reality never existed. Measurements on water samples from all oceans by [55] were averaged and referred to atruly existing reference sample, NBS1, that time available at theUS National Bureau of Standards (NBS). In this way theisotope water standard, SMOW, became indirectly defined by [58] as:
18

A -10
-12 -14
Meuse

12 2 4

8 10 12 2 4 1968

6 8 10 12 2 4 1969

8 10 12

1967 -6
18

(H 2O) ()
Meuse

-7

NBS1 / SMOW= 7.94

-8 -9 -10 -11
Rhine

TheInternational Atomic Energy Agency (IAEA), Section of Isotope Hydrology, in Vienna, Austria and theUS National Institute of Standards and Technology (NIST, theformer NBS) have now available for distribution batches of well preserved standard mean ocean water for use as astandard for 18O as well as for 2H. This standard material, VSMOW, prepared by H. Craig to equal theformer SMOW as closely as possible both for 18 and 2, has been decided by an IAEA panel in 1976 to replace the original SMOW in fixing thezero point of the18 scale. All water samples are to be referred to this standard. From an extensive laboratory intercomparison it became clear that thedifference between theearly SMOW and thepresent VSMOW is very small [59], probably:
18

Fig. 7.8. A three-year observation of the isotopic composition of water from the N.W. European rivers Rhine and Meuse [50]: A . 13 values of the dissolved bicarbonate fraction, showing normal values during winter and relatively high values in summer, probably because of isotopic exchange of thesurface water bicarbonate with atmospheric CO2. B. 18 values, where the river Meuse is showing the average value and the seasonal variations of 18 in theprecipitation: high values in summer, low during winter; during early spring and summer theRhine receives meltwater from theSwiss Alps with relatively low 18 because of thehigh-altitude precipitation .

SMOW / VSMOW = +0.05

(7.20)

At present two standard materials are available for reporting 18 values, one for water samples, one for carbonates. This situation arises from thepractical fact that neither theisotope measurements on water nor those on carbonates are performed on theoriginal material itself, but are made on gaseous CO2 reacted with or derived from thesample. Thelaboratory analysis of O/ O in water is performed by equilibrating awater sample with CO2 of known isotopic composition at 25C (Sect. 10.2.1), followed by mass spectrometric analysis of this equilibrated CO2 (Sect.11.1). This equilibration is generally carried out on batches of water samples, consisting of theunknown samples (x) and thestandard or one or more reference samples. After thecorrection discussed in Sect.11.2.3.4 is made, it is irrelevant
18 16

whether thewater samples themselves are being related or theCO2 samples obtained after equilibration, provided sample and standard are treated under equal condition:
18

x / VSMOW = 18xg / VSMOWg

(7.21)

where g refers to theequilibrated and analysed CO2. Theabsolute 18O/16O ratio of VSMOW is reported as (2005.2 0.45) 106 [60]. Reference and intercomparison samples are available from theIAEA and theNIST. Asurvey of thedata is given in Table 11.2. In order to overcome small analytical errors, some laboratories prefer to fix their VSMOW scale by two extreme 63

INTRODUCTION

TABLE 6.3. Thestable isotopes of oxygen: practical data for thenatural abundance, properties, analytical techniques and standards.
16

17

18

stability natural abundance abundance range in hydrological cycle reported as in instrument analytical medium usual standard deviation international standard with absolute value

stable 0.9976

stable 0.00038 15
17

stable 0.00205 30
18

or 17O
MS O2

or 18O
MS

CO2 or O2 0.05 VSMOW for water VPDB for carbonate etc VSMOW: 0.0020052 VPDB: 0.0020672

Note: MS= mass spectrometry. Further details are given in Sect.7.2, and in Chapters 10 and 11.

for water for carbonate

18 18

VSMOW ()
0 +20

VPDB ()

60 ocean water arctic sea ice marine moisture (sub)tropical precipitation Dead Sea/Lake Chad temperate zone precipitation Alpine glaciers Greenland glaciers Antarctic ice Quatern. marine carbonates fresh-water carbonates ocean water marine carbonates igneous rocks marine atmospheric CO 2 atmospheric oxygen organic matter

40

20

20

+20
18

+40
VSMOW

+60

()

Fig. 7.9. General view of 18O/16O variations in natural compounds. Theranges are indicative for themajority of materials shown. Therelation between theVPDB and VSMOW scales is given in Sect.7.2.3 and Fig.7.11.

64

natural abundance of thestable isotopes of C, O and H

TABLE 6.4. Oxygen isotope fractionation in theequilibrium system CO2H2OCaCO3.

t (C) 0 5 10 15 20 25 30 35 40
18

18 18

sg/s=+ 10.25 sg/lg=19082/T 65.88

18

(7.19)

[51]: 18i/l=+ 3.5 (0C); 18i/v=+ 15.2 (0C);

e

v/l ()

18

s/l ()

18

g/l ()

18

g/lg ()

18

sg/lg ()

i/v= + 16.6 (10C)

11.55 11.07 10.60 10.15 9.71 9.29 8.89 8.49 8.11

+34.68 +33.39 +32.14 +30.94 +29.77 +28.65 +27.56 +26.51 +25.49

+46.56 +45.40 +44.28 +43.20 +42.16 +41.15 +40.18 +39.24 +38.33

+5.19 +4.08 +3.01 +1.97 +0.97 0 0.93 1.84 2.71

+3.98 +2.72 +1.51 +0.34 0.79 1.88

()
40
CaCO3 solid

50
CO2 gas g/l

2.93 3.96 4.94

30
s/l

18

Note:18y/x represents thefractionation of compound y relative to compound x, and is approximately equal to y - x. Values for intermediate temperatures may be calculated by linear interpolation (Fig.7.9). T=t (C) + 273.15 K l=liquid H2O , v=H2O vapour , i=ice , g=gaseous CO2 , s=solid CaCO3 , lg=CO2 (g) isotopic equilibrium with H2O (l) at 25C , sg=CO2 (g) from CaCO3 (s) by 95% H3PO4 at 25C.

fractionation

20

10
H 2O liquid

0
v/l H 2O vapour

-10

-20 0 10 20 temperaturet ( C) 30 40

[55]: ln18v/l=1137/T2 + 0.4156/T + 0.0020667 (7.14a) Values at higher temperatures can be obtained from [52]. Thefractionation between vapour and liquid water is independent of theNaCl concentration of thesolution, contrary to some other salts [53]. From c and e and [53]:18s/l=19668/T 37.32 (7.15) [54]: 18g/l=17604/T 17.89 (7.16) From c, where lg is obtained from l by applying the18g/l value at 25C (concluded by an IAEA panel to be +41.2
18

1/T adjustment:8v/l=7356/T + 15.38 (7.14b)

Fig. 7.10. Temperature dependent equilibrium fractionations for oxygen isotopes of water vapour (v), gaseous CO2 (g), and solid calcite (s) with respect to liquid water (l).

b c d

points (Sect. 11.2.3.5). Using this procedure, thesample 18 is located on alinear scale between VSMOW (0) and SLAP (Standard Light Antarctic Precipitation) with adefined value of
18 18

g/lg=16909/T 56.71

(7.17)

SLAP / VSMOW =55.5 (7.22)

This fractionation is independent of thesalt content of thesolution [55, 56]:t(C)=16.5 4,3(18s 18w) + 0.14(18s 18w)2 (7.18)

where 18 refers CO2 prepared from solid carbonate with 95% H3PO4 at 25C and 18w to CO2 in isotopic equilibrium with water at 25C, both relative to VPDB-CO2 sg is obtained from s by applying thefractionation for theCO2 production at 25C

values of carbonates are given with reference to thesame PDB calcite used for 13C (Sect. 7.1.3). Thezero point of this PDB scale was fixed by means of theNBS20 reference sample (Solenhofen limestone) which originally was defined as [40]:
18

NBS20 / PDB=4.14

Theabsolute 18O/16O ratio of PDB-CO2 was originally reported as 0.0020790 [40]. 65

INTRODUCTION

This value, however, does not agree with Baertschis ratio for VSMOW and theaccurately measured difference between thetwo standards (Fig. 7.10). At present avalue of 0.0020672 is considered to be more realistic (Table11.1). Recently, samples from NBS20 do not always show theabove value. Probably because of exchange with atmospheric vapour due to improper storage, the18 value may have shifted to close to 4.4. Therefore, anew set of carbonate reference materials has been introduced by theIAEA where NBS19 replaces NBS20. TheVPDB (Vienna PDB) scale has now been defined by using NBS19:
18

Henceforth, all 18 values of carbonates are reported relative to VPDB, 18 of gaseous (atmospheric) CO2 relative to VPDB-CO2, and all 18 values of water relative to VSMOW, unless stated otherwise. More details on themeasurement and calculation procedures are given in Chapter 11. 7.2.4.
18

Survey of natural 18O variations

variations throughout thehydrologic cycle will be discussed in detail in theother volumes. Here we present only abroad survey (Fig.7.12). 7.2.4.1. Seawater Theoceans form thelargest global water reservoir. The18O content in thesurface layer is rather uniform, varying between +0.5 and 0.5 [55]. Only in tropical and polar regions larger deviations are observed. In tropical regions more positive values are caused by strong evaporation: 18 of water in theMediterranean amounts to +2 (2=+10). In polar regions more negative values originate from water melting from isotopically light snow and ice. If ocean water were evaporating under equilibrium conditions, thevapour resulting would be 8 to 10 depleted in 18O, depending on temperature. However, oceanic vapour appears to have an average 18 value of 12 to 13, which must partly be due to kinetic fractionation. Therelative humidity of theair and theevaporation temperature influence theamount of non-equilibrium fractionation occurring (see Volume 2 on Precipitation). 7.2.4.2. Precipitation Thetransformation of atmospheric water vapour to precipitation depends on so many climatological and local factors, that the18 variations in precipitation over theglobe are very large. As ageneral rule 18 becomes more negative thefurther therain is removed from themain source of thevapour in theequatorial regions. In theArctic and Antarctic, 18 of theice can be as low as 50. This gradual 18O depletion model is schematically shown in Fig.7.13.

NBS19 / VPDB = 2.20 (7.23)

Thecarbonate itself is not analysed for 18 but rather theCO2 prepared according to astandard procedure which involves treatment in vacuum with 95% (or 100%) orthophosphoric acid at 25C. If samples and reference are treated and corrected similarly,
18

x / VPDB = 18xg / VPDBg

(7.24)

where g refers to theprepared and analysed CO2, so that neither thefractionation between thecarbonate and theCO2 prepared from it (Table7.4) nor thereaction temperature need to be known. Therelations between theVPDB, VPDBCO2 (VPBDg), VSMOW and VSMOW-CO2 (VSMOWg) scales are derived from theequations given in Table7.4, according to Eq.7.24:
18

x / VSMOW = 1.03086 18x / VPDB + 30.86 (7.25) x / VSMOW = 1.04143 18x / VPDBg + 41.43 (7.26) x / VSMOWg = 1.00027 18x / VPDBg + 0.27 (7.27)

18

18

Therelations are visualised in Fig.7.11.These are of interest in isotope studies on silicates, oxides, carbonates, organic matter, and their correlation with water. Theconversion equations are in general:
18

lower = i 18upper + i

(7.28)

where i=D , D , or , and lower and upper refer to thelevels in thescheme. 66

natural abundance of thestable isotopes of C, O and H

In Volume 2 thevarious effects will be discussed in detail, causing regional and temporal variations on 18 of precipitation. We can distinguish between: (1) latitudinal effect with lower 18 values at increasing latitude (2) continental effect with more negative values for precipitation themore inland
18

(3) altitude effect with decreasing 18 in precipitation at higher altitude (4) seasonal effect (in regions with temperate climate) with more negative 18 values during winter (5) amount effect with more negative 18 values in rain during heavy storms.

VPDB-CO 2 VSMOW-CO 2 NBS19-CO 2

0.27 0.99973 1

Dc 2 0.99780 0.99807 2.20

VPDB NBS19

1 1.01025
Dc 0.99780 2.20

VSMOW

2 1.0412

3 1.0309

4 1.0415

SLAP-CO 2

Dw 0.94450 55.50

SLAP

Dw 0.94450 55.50

Fig. 7.11. Relations between 18O reference and intercomparison samples with respect to VPDB and VSMOW [61]. VPDB-CO2 refers to CO2 prepared from hypothetical VPDB by treatment with H3PO4 (95%) at 25C, VSMOWCO2 to CO2 equilibrated with VSMOW at 25C. Thevertical scale is indicative and not entirely proportional to real numbers. 1 : Difference between VPDBCO2 and SMOWCO2 (0.22) [62, 45] plus the difference between SMOW(CO2) and VSMOW(CO2) (0.05) (Eq.7.20) Dc : defined value of NBS19 relative to VPDB (Eq.7.24) 2=Dc 1 1 : according to [53] 2 : average of 3 independent methods applied by 4 different laboratories 3: from 2 , 1 , and 1; 1.03086 is theexact figure quoted by [53], in agreement with 2=1.04115 [54] 4: f from 3 and 1

67

INTRODUCTION

7.2.4.3. Surface water In Fig. 7.8 some data are shown on variations in riverwater. Theseasonal variation with relatively high values in summer is characteristic for precipitation in temperate regions. Thebasis of both curves represents theaverage 18 values of precipitation and groundwater in therecharge areas, i.e. N.W. Europe (Meuse) and Switzerland/S.Germany (Rhine), thelatter with alarge transport of relatively isotopically light meltwater in spring.
18

tion can be derived (Volume 2) which comes to thetemperature dependence [16, 66]: d18 / dt +0.7 / C (7.30) By this relation it is possible to translate isotope variations into climatic variations during geologic times. Records have been obtained on ice cores from Greenland and theAntarctic, showing thealternation of low-18 (or low-2) and high-18 (or high-2) periods, respectively cold and warm periods (Eq.7.30). 7.3. Relation between 13C and 18O variations in H2O, HCO!, and CO$ Differences and therelations between thevarious natural water-carbonate systems can nicely be displayed by considering both 18 of thewater and 13 of thedissolved bicarbonate. Fig.7.15 is aschematic representation of three waters of realistic isotopic composition, each provided with thetemperature dependent range of calcite precipitated under equilibrium conditions. This figure essentially is acombined graph of Figs 7.5 and 7.12. From an isotopic point of view, the4 common types of water are: (1) Seawater, with 18 values around 0 (by definition) at present; the carbonate range is that of recent marine carbonates. Because of changing glacial and interglacial periods the 18 of ocean water varied in thepast. Also the18 values of marine limestone have increased during thecourse of geological time, while the13 values have essentially remained thesame [68]. (2) Ground- and river water, with an arbitrarily chosen value of 18. In freshwater bicarbonate 13 generally is around 11 to 12. Theisotopic compositions of fresh-water carbonates derived from this water may result from theknown equilibrium fractionations (Tables 6.2 and 6.4), in asimilar way as is indicated for marine carbonate. (3) Stagnant surface or lake water can be subjected to processes altering theisotopic composition. Provided thewater has asufficient residence time in the basin, isotope exchange will cause the13C content to reach isotopic equilibrium with atmospheric CO2.

Evaporation, especially in tropical and semi-arid regions, causes 18O enrichment in surface waters. This results, for instance, in 18 of theriver Nile to be +3 to +4, and of certain lakes as high as +20 (Sect.4.4.5 and 7.5). 7.2.5. Climatic variations

Theslow precipitation of calcium carbonate is aprocess during which carbonate and water are in isotopic equilibrium, as was pointed out earlier. The18O content of thecarbonate is, therefore, primarily determined by that of thewater. Thesecond determining factor is thetemperature, as is indicated in Fig. 7.10. Consequently we can in principle deduce thewater temperature from 18 of carbonate samples in marine sediment cores, provided 18 of thewater is known ( 0). This was originally believed to be thebasis of the18O palaeothermometry of fossil marine shells [63]. Thepresent-day opinions assume avarying 18 of thesurface ocean water during glacial/interglacial transitions [64, 65], due to varying amounts of accumulated ice with low 18 as polar ice caps. As arealistic order of magnitude, an estimated amount of 5105km3 of ice (=Vice) laid down especially on thenorthern polar ice cap during thelast ice age with an average 18 value of 20 changes the18 value (at present=0) of the107km3 of ocean water (= Vocean) by +1, as is simply deduced from themass balance: Vpresent ocean 18 present seawater =Vce-age ocean 18ice-age 18 (7.29) seawater + Vice caps ice Another spectacular application of isotope variations in nature is thededuction of climatic changes in thepast from 18O/16O or 2H/1H ratios in polar ice cores. If theprocess of gradual isotope depletion of precipitation is studied in detail as afunction of latitude and thus of air temperature, arela68

natural abundance of thestable isotopes of C, O and H

marine freshwater carbonate 5C 25C

ocean water tropical preci pitation

river/lake

ocean

arbitrary freshwater

evaporation

18

VSMOW

increasingly depleted precipitation

equatorial marine vapour

polar

high

temperate low

tropical precipitation

increasingly depleted vapour

water vapour equilibrium kinetic

higher latitudes lower temperatures

ocean water

25

20

15

10

5 for water : for carbonate:

18

0 +5 VSMOW () 18 VPDB ()

polar precipitation air temperature

Fig. 7.12. Schematic survey of natural 18 variations in nature, especially relevant in thehydrological cycle. Themarine vapour gradually becomes depleted in 18O during the transport to higher latitudes (Fig.7.13). Evaporation of surface water may cause thewater to become enriched in 18O. Finally theformation of solid carbonate results in a shift in 18 depending on temperature (cf. Fig.7.5).

Fig. 7.13. Schematic representation of the gradual depletion in 18O of atmospheric water vapour and the condensing precipitation, the further the vapour and precipitation process are removed from themain source of the vapour: the tropical marine belt. At lower temperatures theisotope fractionation between water vapour and liquid water is larger, counteracting but loosing from the Rayleigh depletion process (cf. Fig.7.7 and 7.12).

Then 13 equals that in theocean. Carbonate and 18 are related to, respectively, HCO! and H2O as indicated for themarine values. The 18O content of thewater, especially in warmer climates, will change towards less negative or even positive values due to evaporation.
13

7.4. Stable hydrogen isotopes 7.4.1. Thenatural abundance

(4) Estuarine water has intermediate values of 13 (HCO!) or 13(DIC) and 18(H2O), depending on thedegree of mixing of theriver- and seawater. Thelatter behaves conservatively, i.e. is only determined by themixing ratio; 13 (DIC) also depends on theDIC values of themixing components. Therefore, themixing line is generally not straight. Therelation with 13 of thebicarbonate fraction is even more complicated, as thedissociation equilibria change with pH (even thepH does not at all behave conservatively) (Sect.9.5.4).

Thechemical element hydrogen consists of two stable isotopes, 1H and 2H (D or Deuterium), with an abundance of about 99.985 and 0.015% and an isotope ratio 2H/1H 0.00015 [69]. This isotope ratio has anatural variation of about 250, higher than the13 and 18 variations, because of therelatively larger mass differences between theisotopes (Fig.7.16). As with 18O, high 2H concentrations are observed in strongly evaporated surface waters, while low 2 H contents are found in polar ice. Variations of about 250 are present in thepart of thehydrological cycle to be discussed here. 69

INTRODUCTION

7.4.2.

Hydrogen isotope fractionations

+1.5 0

18
marine carbonate Arctic ice 0 40 36 Antarctic ice 49 45

Themost important hydrogen isotope fractionation is that between theliquid and thevapour phases of water. Under equilibrium conditions water vapour is isotopically lighter (contains less 2H) than liquid water by amounts given in Table 7.6. Fig. 7.3 shows some actual isotope ratios of equilibrium systems and thematching 2 values. Thefractionation by diffusion of H2O through air (2d) varies between 22.9 1.7 [57] and 20.4 1.4. (unpubl.), slightly more than thevalue calculated from Eq.3.34 (16.3) (cf. Sect. 7.3.2). 7.4.3. Reporting 2H variations and the2H standard

20

40

60

80 (10 years BP) Fig.Time 7.14. Palaeotemperature records represented 18 by variations in time in the CaCO3 fraction from foraminifera shells in deep-sea core sediments (left), in glacier ice of a Northern Greenland glacier (at Summit), and in glacier ice of an Antarctic ice core (at Vostok), respectively from left to right (figure modified from [67]). In each record theleft side indicates thelower temperatures, for instance, at 20000 years BP each curve shows the most recent glacial maximum. The upper 10000 years contain the present warm interglacial, theHolocene.
3

VSMOW is thestandard for 2H/1H as it is for O/16O ratios. Values for theabsolute 2H/1H ratio of VSMOW and SLAP are reported to be (155.76 0.07)106 and (89.02 0.05)106, respectively, by [70], (155.75 0.08) 106 and (89.12 0.07)106 by [71], and (155.60 0.12)106 and (88.88 0.18)106 by [72].
18

Theaverage 2 value of thesecondary standard SLAP on theVSMOW scale (Sect.7.2.3) consequently is 428.2 0.1. Based on these data the2 value has been defined as:
2

7.4.4.

SLAP / VSMOW = 428.0 (7.33)

Survey of natural 2H variations

No significant difference in 2 has been detected between theoriginal SMOW standard and VSMOW [59]. Reference and intercomparison water samples are available from theIAEA (Table11.3). The2H contents of hydrogen-containing samples are determined by completely converting them to hydrogen gas. Therefore, fundamental problems of isotope fractionation during sample preparation, as with 18O, do not occur; however, theanalyses are more troublesome (Sect.10). Henceforth all 2 values will be reported relative to VSMOW. More details on themeasurement and calculation procedures, and on isotope reference samples are given in Chapter 10. 70

From theforegoing it is evident that some correlation should exist between 2H and 18O fractionation effects. Therefore, in natural waters arelation between 2 and 18 values is to be expected. Indeed, the2 and 18 variations in precipitation, ice, most groundwaters and non-evaporated surface waters have appeared to be closely related. Therefore, thequalitative discussion given in Sect.7.2.4 for 18 applies to 2 equally well. Thenext section is devoted to this relation. 7.5. Relation between 2H and 18O variations in water If we simply assume that evaporation and condensation in nature occur in isotopic equilibrium, therelation between the2 and 18 values of natural waters is determined by both equilibrium fractionations 2v/l and 18v/l. In Table7.6 theratio

natural abundance of thestable isotopes of C, O and H

lake
0

25 C 5 C evaporation ocean

VPDB ()

exchange with atm. CO2

13

estuarine mixing of DIC

H 218O / H 13CO 3 Ca 13C 18O 16O 2

10

rivers

10

5
18

0 VPDB , 18 VSMOW ()

Fig. 7.15. Relation between thenatural variations of 13(HCO! and CaCO3) and 18(H2O and CaCO3). Thegraph is essentially acombination of Figs.7.5 and 7.12. Estuarine mixing only results in astraight line between theriver and sea values of 13DIC, if CT of thecomponents is equal. Because this is rarely thecase, therelation between thetwo members mostly is observed as aslightly curved line. Additionally, 13(HCO!) in estuaries is not subject to conservative mixing, because themixing process rearranges thecarbonate fractions (Sect.9.5.4). Depending on theresidence times of thewater at thesurface, evaporation and isotope exchange changes theisotopic composition to higher values.

ocean water arctic sea ice marine moisture (sub)tropical precipitation temperate zone polar ice Alpine glaciers Lake Chad wood cellulose temperate peat zone clay minerals 200 150 100 50 VSMOW ()
0 + 50

Fig. 7.16. General view of 2H/1H variations in natural compounds. Theranges are indicative for themajority of materials shown.

71

INTRODUCTION

TABLE 6.5. Thestable and radioactive isotopes of hydrogen

1

natural abundance stability natural specific activity decay mode / daughter half-life (T1/2) decay constant () abundance range in hydrological cycle reported as in instrument analytical medium usual standard deviation international standard with absolute value

0.99985 stable

0.00015 stable

< 1017 radioactive < 1,2 Bq/L water / 3He 12.320 0.022 a 5.576102/a= 1/18.33 a1 18 keV

250
2

0 to 1016
3

or 2H or D MS H2 0.5 VSMOW

TU, Bq/L H2O PGC, LSS H2O, C2H6, C6H6 1% at high level NBS-SRM 4361 H/1H=6600 TU or=0.780 Bq/g H2O as of Jan.1, 1988
3

H/ H=0.00015575
1

Note: Practical data for thenatural abundance, properties, analytical techniques and standards. Further details are given in Sect.7.4 and 8.3, and in Chapters 10 and 11. MS=mass spectrometry, PGC=proportional gas counting, LSS=liquid scintillation spectrometry, AMS=accelerator mass spectrometry.

TABLE 6.6. Hydrogen isotope fractionation in theequilibrium system liquid water (l), water vapour (v), and ice (i)
t (C) 0 5 10 15 20 25 30 35 40
2

Note: y / x represents thefractionation of compound y relative to compound x and is approximately equal to 2 (y) 2(x). Values for intermediate temperatures may be obtained by linear interpolation; T=t (C) + 273.15 K.
a

v/l a() 101.0 94.8 89.0 83.5 78.4 73.5 68.9 64.6 60.6

18

v/l ()

v/l / 18v/l b 8.7 8.55 8.4 8.25 8.1 7.9 7.75 7.6 7.4

11.55 11.07 10.60 10.15 9.71 9.29 8.89 8.49 8.11

[51]: ln2=24844/T2 + 76.248/T 0.052612 (7.31a) 1/T adjustment: 2v/l=85626/T + 213.4 (7.31b)

Values at higher temperatures can be obtained from [52]. Theratios between thefractionations for 18O and 2H at theliquid-vapour equilibrium are obtained from [51]:2i/l=+ 19.3 (at 0C) (7.32)

72

natural abundance of thestable isotopes of C, O and H

+ 40
meteoric water line: 2 = 8 18 + 10

ocean
rain condensation water

VSMOW ()

40

80

marine atmospheric vapour at equator

water vapour in equilibrium at 200C

120
remaining vapour

160

20

16

12
18

8 VSMOW ()

+4

Fig. 7.17. Relation between natural variations of 18 and 2 ocean water, atmospheric vapour and precipitation. Theblack round represents thehypothetical value of water vapour in isotopic equilibrium with ocean water, black square theobserved isotopic composition of equatorial marine vapour, originated from themore realistic nonequilibrium fractionation. Marine vapour gradually condenses into precipitation (hatched arrow) with apositive fractionation, leaving thevapour progressively depleted in 18O and 2H (grey arrow) (cf. Fig.7.13).

of these factors is presented for thetemperature range of 040C. [73, 16] found arelation between the2 and 18 values of precipitation from various parts of theworld:
2

=s18 + d (7.35)

= 8 18 + 10

(7.34)

This relation, shown in Fig. 7.17 has become known as theGlobal Meteoric Water Line (GMWL) and is characterised by aslope of 8 and acertain intercept with the2H axis (=the2 value at 18=0). Thegeneral relation is of theMWL is:

where theslope s=8, as is explained by theratio between theequilibrium isotope fractionations of hydrogen and oxygen for therain condensation process (Table7.6); d is referred to as thedeuterium excess (d-excess), theintercept with the2 axis. In several regions of theworld as well as during certain periods of theyear and even certain storms the2 value is different from 10, depending on thehumudity and temperature conditions in theevaporation region. Theisotopic composition of water vapour over seawater with 2=18=0 vs VSMOW is 73

INTRODUCTION

somewhat lighter than would follow from isotopic equilibrium with thewater: theevaporation is anon-equilibrium (partly kinetic) process. However, from theobserved vapour composition onward thevapour and precipitation remain in isotopic equilibrium, because theformation of precipitation is likely to occur from saturated vapour (i.e. vapour in physical equilibrium with water). Consequently the18 and 2 values both move along themeteoric water line (Eq.7.33). In Volume 3 (Surface Water) certain circumstances will be discussed leading to deviations from thecommon MWL. For instance, larger values of d are occasionally observed.

Apart from this, deviations occur in evaporating surface waters, showing slopes of 4 to 5 rather than 8. If 2o and 18o denote theoriginal isotopic composition of an arbitrary surface water, the values after evaporation are related by: 2o 4.5 (18 18o)or2 4.5 18 (7.36)
2

(Fig.7.18). Therelease of relatively low- water vapour to theair results in aincrease in of theremaining water, as illustrated by themodel of Sect.4.4.5, here for 2 as well as 18.

+ 20
meteoric water line:
2

= 8 18 + 10

ocean water

VSMOW ()

estuarine mixing

20

arbitrary freshwaters evaporated water 2 = 4.5 18 escaping vapour

40

60

80

10

18

4 VSMOW ()

+2

Fig. 7.18. Relation between 18 and 2 for estuarine mixing and for evaporating surface water. Because theevaporation is anon-equilibrium process, isotope fractionations involved are not necessarily related by afactor of 8, as is theequilibrium condensation process, thebasis for themeteoric water line (Fig.7.17). As in thepreceding figure, thearrows indicate thedirection of change of theisotopic composition of theescaping vapour and of theremaining evaporated water.

74

8. NATURAL ABUNDANCE OF RADIOACTIVE ISOTOPES of C and H

In this chapter thetwo nuclides, 14C and 3H, will be treated that are themost relevant in thehydrological cycle. Chapter 12 contains asurvey of theisotopes with less extensive applications. 8.1. Theradioactive carbon isotope 8.1.1. Origin of 14C, decay and half-life

C thus formed very soon oxidises to 14CO, and ultimately to 14CO2 which mixes with theinactive atmospheric CO2 (Fig. 8.1). Through exchange with oceanic dissolved carbon (primarily bicarbonate), most 14CO2molecules enter theoceans and living marine organisms. Some are also assimilated by land plants, so that all living organisms, vegetable as well as animal, contain 14C in concentrations about equal (Sect.8.1.3) to that of atmospheric CO2.
14 14

Thenatural occurrence of theradioactive carbon isotope, 14C or radiocarbon, was first recognised by [74]. It is naturally formed in thetransitional region between thestratosphere and troposphere about 12km above theearths surface through thenuclear reaction:
14

C decays according to: C 14N + (8.2)

14

N + n 14C + p

(8.1)

Thethermal neutrons required are produced by reactions between very high-energy primary cosmic ray protons and molecules of theatmosphere.

with amaximum - energy of 156 keV and ahalflife of 5730 40 years [75] (Fig.8.2). Originally thehalf-life was thought to be 5568 years, so that during thefirst decade or two 14C age determinations were based on thewrong half-life. Later, when thebetter half-life became known, so many 14 C ages were already published that, in order to avoid confusion, it was decided that theoriginal

cosmic radiation

14

N+n

14

C+p

14

14

N +
14

14

14

14

CO 2

12

CO 2

12

CO 2 fossil fuel nuclear bomb exchange LAKE

exchange

assimilation

H14CO 3

OCEAN

shells Ca14 CO 3 ageing

humus 14CO 2 groundwater table

12 + Ca12CO 3 + H 2O H 14CO 3 + H CO 3

Fig. 8.1. Origin and distribution of 14C in nature. Thenatural 14C concentration by theproduction by neutrons from cosmic radiation has been influenced by chronologically theaddition to theair of CO2 without 14C by thecombustion of fossil fuels and theproduction of 14C by neutrons released by thefission and fusion reactions during nuclear explosions.

T1/2 = 12.43 a

INTRODUCTION

18 keV Emax = Emax = 156 keV Emax = 18 keV

14 He N 3 14 He 3 14 A Anatural = 250 Bq / k 3 natural = 0.6 Bq / liter H2O 14 14 Anatural = 0.6 Bq / liter H2O 14C activity, that is the A half-life should continued to be used3 for reporting Cnatural = 250 Bq / The absolute (specific) 14 He N 14 C ages. Moreover, it was meanwhile known that radioactivity (in Bq or, conventionally, in disinte3 ages would still be in even using theright Anatural = error, 0.6 Bq / liter H2 O grations per14 minute of carbon) is Anatural(dpm) = 250 per Bq gram / kg C Fig.8.2 Decay schemes of tritium and radiocarbon. Both nuclides are pure half-life, because of thenatural variations in Fig.8.2 Decay schemes of tritium and radiocarbon. Both nuclides are pure given thesymbol specific activities are given as 3A and 14A. the 14C content of atmospheric CO2 during geo-present-day present-day specific activities are given as 3A and 14A. 14 a=number of disintegrations minute logicFig.8.2 times and deviating from thepresent. These Decay schemes of tritium and radiocarbon. Both nuclides are pure per emitters. The 14 (dpm/gC) (8.3) errors were even larger. Nowadays the C cali3 14 present-day specific activities are given as A and14 A. C activity, that is the 14 C radioactivity (in Bq or, conve The absolute of tree (specific) 14 bration, based on theknown 14C content 14 The absolute (specific) C activity , that is the an C radioactivity It is extremely difficult to make absolute mea- (in Bq or, conv rings with exactly known age, removes both er- per minute (dpm) disintegrations gramMoreover, of carbon)theabsolute is given the symbol of(dpm) a14C per activity. disintegrations surement per minute per gram of carbon) is given the symbol rors at once (Sect.8.1.4). 14 14 14 14 C content asample is generally not(dpm/gC) relevant. The absolute (specific) C activity, that is the C radioactivity (in Bq or, conventionally, in A= number ofof disintegrations per minute 14 14 A = number of disintegrations per minute (dpm/gC) Theproduction and distribution of C in nature Therefore, thesample activities are compared disintegrations per minute (dpm) per gram of carbon) is given the symbol occurs through series of chemical and It biological is extremely with difficult to make absolute In measurement of a 14 C activity. M theactivity ofan astandard. reality, thenumIt is extremely difficult to make an absolute measurement of a 14C activity. M 14 14 14 14 processes which has become stationnary throughA = number of disintegrations per minute (8.3) ber of Csample registrations ( registrations from C C content of(dpm/gC) a is generally not relevant. Therefore, the sample absolute 14 absolute C content of a sample is generally not relevant. Therefore, the sample out much of geologic time. As aconsequence, decay in radiometric detectors such as propor14 standard. In reality, the number of 14 C reg compared with the activityof ofa a It is extremely difficult to make an absolute measurement activity. Moreover, the number of 14 C re compared the activity of aCstandard. In reality, the C in theatmosphere, oceanswith theconcentration of 14 tional counters and liquid scintillation counters, 14 registrations from C decay in radiometric detectors such as proportional counte 14 14 absolute 14 C content of a samplevalue is generally not relevant. Therefore, the sample activities are and biosphere reached asteady-state which registrations C concentration in AMS sysregistrations from C decayof in radiometric detectors such as proportional count 1414 CC concentration in AMS systems) are r registrations of has been almostwith constant ageologic period counters, 14 tems) are related to thenumber of registrations registrations ( compared the during activity of scintillation ascintillation standard. In reality, the number of counters, registrations of C concentration in AMS systems) are 14 which is long compared to thelife span of a number ofC registrations from the standard under equal from such thestandard under equal conditions. registrations from 14C decay in radiometric detectors as proportional counters andconditions. liquid number conditions. C/C, 14 is of ofregistrations from the14standard under equal nucleus. This natural concentration, 14 14 14 14 C concentration in in AMS systems) are related toconcenthe scintillation counters, registrations of results a or C activity ratio or C This results in aThis C activity ratio C concentration ratio : , which is equivalent to aspetheorder of 1012 This results in a 14C activity ratio or 14C concentration ratio: tration ratio : from (disintegrations the standard under equal conditions. cific number activity of registrations about 0.25 Bq/gC 14 14 Asample 14 A 14 14 per second per gram of A 14 carbon) (Sect.5.3). 14 A= a = = sample 14 This results in a C activity ratio or C concentration a =1414A ratio: =1414A = reference R Areference AR 14 14 14 Asample A 8.1.2. Reporting 14 14 14 a = 14 C variations = = and C concentration in the samp C decay rate in the sample 14 14 = 14 C decay rate in the sample = 14 C concentration in the samp the14C standard Areference 14 AR = 14 C decay rate in the reference = 14 C concentration in the referen C decay rate in the reference C concentration in the refere 14 Three modes of reporting C activities are in use, 14 14 C decay rate in the sample C concentrat ion in the sample in part analogous to = theconventions Because internationin the nominator and denominator of the last two fractions the detection Because in the = nominator and denominator of the last two fractions the detectio 14 14 C decay rate are in the reference C concentrat ion in the reference (8.4) ally agreed (IAEA) for stable isotopes [76, 77]. cancelled being equal for sample and reference material, the use of the are cancelled being equal for sample and reference material, the use of th adequate for any of measuring Because in the nominator and denominator of thetype last fractions technique. the detection efficiencies adequate for any typetwo of measuring technique. are cancelled being equal for sample and reference material, the use of the ratio 14a is adequate for any type of measuring technique. 14C T1/2 = 5730 a

Emax = 18 keV

T1/2 = 12.43 a E
max

127

max

= 156 keV

= 18 keV

3 3

He
14

14

A natural = 0.6 Bq / liter H 2O

A natural = 250 Bq / kg C

Fig. 8.2. Decay schemes of tritium and radiocarbon. Both nuclides are pure emitters. Thepresent-day specific activities are given as 3A and 14A.

76

each the as same atmospheric between C3 plants such as trees (13 25) and assimilating a C4 plant such sugar cane (13 CO 10), 2. Therefore, in defining the st 14 Chapitre 8 CO2also in our treatment ofthe all standard C data, we have to normalise the 14C resu each assimilating the same atmospheric . Therefore, in defining activity, but 14 13 value. In Chapter 11 we will go into more detail. Here we suffice also in our treatment of all 14C data, we have to normalise the C results to the same

14 14 14 have be corrected for a deviati international agreement all C tauxdedcr oissancede l ' chantillo n more CRADIOACTIVE concentrat ion dans nstating ' chantillo value. In Chapter 11 NATURAL we will go into detail. Here we l suffice byresults thattoby ABUNDANCE OF ISOTOPES of C C and H = 14 = 14 14 13 C tauxdedcr oissance de la C concentrat ion for dans la rfrence 25, with theaexception of Ox1 has to be corrected to 19 international agreement all Crfrence results havefrom to be corrected deviation of the which value

14 (8.4) from 25, the exception ofdenominator Ox1 which has to corrected to 19. content of carbon naturally growing plants. Because in with thenominator and of The C be standard activity or in concentration was chosen to represent as clo 14 14 14 the last two fractions the detection efficiencies C standard activity does not need to be, in The 14 Cdernires contentto of carbon in naturally growing plants. Parce que, dans et le dnominateur des deux fractions, lefficacit The le Cnominateur standard activity or concentration was chosen represent as closely de as possible the The C standard activi 14 are cancelled being equal for sample and referfact it is not, equal to the C activity of thestan14 14 la dtection14 est annule carcarbon gale pour lchantillon leplants. matriel deit rfrence, lutilisation duactivity be, in fact is not, equal to the C of standard. 14 C content of in growing The C Thedefinition standard activity does not need 14 the a iset adequate ence material, theuse ofnaturally theratio dard. of thestandard Cto activity is The definition 14 14 14 rapport a est tout typeto de technique de mesure. activity is based on 95% the activity the original NBS oxali be, in fact it pour is equal the C activity of the standard. The definition ofspecific the standard Cof foradquate any type ofnot, measuring technique. based on 95% ofof thespecific activity of theorigi 14on 95% of the specific activity 14 nal NBS acid (Ox1) in theyear year AD1950 (Karln et al., 1966), as will be in more detail later activity is based of the original NBS oxalic acid (Ox1) indiscussed the AD1950 Ainsi donc, le symbole A doit tre utilis pour la teneur en C oxalic (radioactivit ou 14 Under natural circumstances thevalues of 14 a [78], as will be discussed in more detail later. a may be used for Henceforth, thesymbol 14 year AD1950 (Karln et al., 1966), as will beThe discussed insoit more detail later. concentration) dun que laorder mthode analytique applique la radiomtrie ou laby: C standard activity is defined 14 are between 0 and 1. In to avoid theuse C chantillon, content (radioactivity or concentration) the 14 C standard activity is defined by: The 14 spectromtrie de masse (SMA). of decimals, itwhether isactivity general practice toby: report these of asample, theanalytical technique C standard is defined The 0 14 0 values in which is equivalent thefactor applied is %, radiometric or mass to spectrometric Astandard = 0.95 14 AOx1 = 13.56 0.07 dpm/gC = 0.226 0.001 Bq/g 2naturelles, les valeurs de 14a sont comprises entre 0 et 1. Afin dviter Sous conditions 10 (see also Sect.11.5.1). It is incorrect to (AMS). 14 0 14 0 0.95 A =14 13 0valeurs .07 dpm/gC = ce 0.226 0.quivalent 001 Bq/gC un (8.6) 14 Astandard 2 (8.6) Ox1 a/10il instead of merely a..56ces dutiliser des write dcimales, est= courant de reporter en %, qui est 2 14 2 14 au lieu de a. Radioactive facteur 10 (voir aussi Part. 11.5.1). Il est incorrect dcrire a/10dpm/gC Isotopesper of Hydrogen Carbon means disintegrations minute and per Radioactive Isotopes of Hydrogen and Carbon In several cases thedifferences in 14C content be0 gram of carbon, while thesuperscript refers to tween theproject samples are small. Therefore, Dans de nombreux cas, les diffrences dans les teneurs en 14C entre les that chantillons dune is valid for the year the fact the definition theuse has been taken over from thestable-isomeans disintegrations per minute gram of carbon, while the supe mme tude sont faibles. Ainsi, lusage a t instaur dpm/gC pour tous les champs des per 1950 only.disciplinaires dpm/gC means disintegrations per minute per gram of carbon, while the supe tope field to define relative abundances, the in casu 14 is valid for the year 1950 only. fact that the definition isotopes de dfinir les abondances relatives, telles que lafact teneur relative en Cis(activit ou the the definition valid supply for the year 1950 only. theoriginal of oxalic acid has - thatBecause the relative 14C content (activity or concentra 14 14 14 concentration) , , et de dfinir la diffrence de teneur en C entre un chantillon et une tion), , defined as the difference between exhausted, batch of oxalic acid exhausted, (Ox2) Because thebeen original supplyanew of oxalic acid has been a new batc Because the original supply of oxalic acid has been exhausted, a new batc 14 C content as afraction of sample and reference is available for distribution by theNIST (formerrfrence, comme une fraction de la valeur de rfrence : (Ox2) is available for distribution by the NIST (formerly US-Nat. Bureau of S (Ox2) is available for distribution by the NIST (formerly US-Nat. Bureau of S thereference value: ly US-Nat. Bureau of Standards). Through careful measurement by a number of laboratories (Mann, 1983), the 14 14 14 A AR A Through careful measurement by a number by of laboratories (Mann, 1983), the Through careful measurement anumber of 14 14 2 = = 1 = a 1 ( 10 %) (8.5) become related to that of the original Ox1 by:has become re14 14 14 C activity laboratories[79], the AR AR become related to that of the original Ox1 by: lated to that of theoriginal Ox1 by: (8.5) 14 0 0 = (1.2736 0.0004) 14 14 AOx2 0 14 AOx1 0 A = ( 1 . 2736 0 . 0004 ) A Ox2 en , ce qui Ox1 (8.7) Les valeurs de sont des petits nombres et sont donc gnralement exprimes Thevalues of are small numbers and there3 est quivalentfore ungenerally facteur 10 (cf.in Part. given , 4.1). which is equivalent Both activities referConsequently to AD1950. the Consequently Both activities refer to AD1950. standard activity is: 3 Both activities refer to AD1950. Consequently the standard activity is: to thefactor 10 (cf. Sect.4.1). thestandard activity is: Dans le Chapitre 7, nous avons vu que lors de nimporte quel processus dans la nature, le 14 0 0 = 0.7459 14 AOx2 (8.8) 14 A 0 14 0 les fractionnement se produit, seulement les isotopes stables mais galement pour standard In Chapter 7 wenon have seen that pour during any process A = 0 . 7459 A standard Ox2 14 cetnot effet introduirait une 14erreur dans isotopes radioactifs que fractionation le C. Ngliger in nature tels isotope occurs, only where the a0 values forla Ox1 and Ox2 refer to 14 0 14 for thestable isotopes but similarly for theradiofor Ox1 and refer to the activity of the m dtermination de lge, parce que la teneur originelle where en C the du matriau serait diffrente de Ox2 14A 0 values theactivity of thematerial in 1950, irrespective for Ox1 and Ox2 refer to the activity of the m where the A values effect active isotope such as 14C. Neglecting this 13 of of irrespective of thetime the of measurement. measurement. celle suppose. Le degr de fractionnement est indiqu par la valeur en time du matriau. Un irrespective of the time of measurement. would introduce an error in an age determina14 les calculation arbres andprocedures exemple est tion, fourni par la diffrence dge apparent entre les on plantes en Con 3 comme Details themeasurement calculationare prothemabecause theoriginal C content of Details the measurement and given in Chapter 1 13 13on the Details measurement and calculation procedures are given in Chapter 1 givenassimilant in Chapter 11. terial would be en different from we assume. ( 25) et les plantes C4 comme lawhat canne sucre ( cedures 10), are chacune 14 A survey of available C reference samples of different compounds and 14 Thedegree of fractionation is nicely indicated 14 nos le mme CO activits mais aussi dans survey standard, of available C reference samplessamples of different compounds and 2 atmosphrique. Ainsi, en dfinissant lesA C reference of difAsurvey of available 13 of thematerial. An example is by the value Table 11.5. 14 13 and traitements des donnes difference C, nous devons normaliser les rsultats la compounds mme valeur deages . is given in Table11.5. 11.5. ferent theapparent in age between CTable 3 plants 13 Dans le chapitre plusand en dtail. Ici, nous nous baserons simplement sur le 14 25) aC4 plant such such11 as nous treesverrons ( cela 8.1.3 SURVEY OF NATURAL 14 13 14 14C VARIATIONS each as un sugar caneinternational, ( 10), fait que, par accord tous les assimilating rsultats tre corrigs dune 8.1.3. Survey of natural C 8.1.3 C doivent SURVEY OF NATURAL C VARIATIONS 13 . Therefore, in defining thesame atmospheric CO variations 2 dviation de la valeur de 25, avec lexception du Ox1 qui lui, doit tre corrig thestandard activity, but also in our treatment of 8.1.3.1 ATMOSPHERIC CO2 19. 8.1.3.1 ATMOSPHERIC CO2 8.1.3.1. Atmospheric CO2 results all 14C data, we have to normalise the14C 13 occur in occur the stationary state mentioned in Sect.8.1 will go fluctuations to thesame value. In Chapter 11 we Certain Certain fluctuations in the stationary state Certain fluctuations occur in the stationary state mentioned in Sect.8. into more detail. Here we suffice by stating that variations in cosmic ray intensity, andBecause in climate affecting the size of the c mentioned in Sect. 8.1.1. of variations variations in cosmic ray intensity, and in climate affecting the size of the c 128 have by international agreement all 14C results the 14 to in cosmic ray intensity, and in not climate affecting of atmospheric carbon has always been precisely the sam 14C content 13 thefrom C content of atmospheric carbon has not always been precisely the sa be corrected for adeviation of the value 14 14 C content thesize of thecarbon reservoirs, the This phenomenon has been observed by measuring the 14C content of tree ring 25, with theexception of Ox1 which has to be This phenomenon has been carbon observed bynot measuring the C content of tree rin of atmospheric has always been precorrected to 19. These fluctuations do not exceed a few This per phenomenon cent over relatively short p cisely thesame as at present. These fluctuations do not exceed a few per cent over relatively short p has beenlittle observed by measuring the14C content was of The 14C standard activity or concentration therefore, very relevance to the hydrologist who is generally therefore, of veryrings little relevance to the hydrologist who is generally of tree (see Fig.8.5). chosen to represent as closely as possibledissolved the14C carbon from a variable vegetation covering a long and uncertain pe dissolved carbon from a variable vegetation covering a long and uncertain pe The strong increase in the atmospheric 14 C level due to the nuclear test explo The strong increase in the atmospheric 14C level due to the nuclear test explo 77 3 relevance to the hydrologist. During the bomb explosions 14 14C (and 3H) is be relevance to the hydrologist. During the bomb explosions C (and H) is be the same nuclear reactions that are responsible for the natural production. the same nuclear reactions that are responsible for the natural production. hemisphere the peak concentration occurred during the spring of 1963, wh hemisphere the peak concentration occurred during the spring of 1963, wh

INTRODUCTION

C content () of atmospheric CO 2

These fluctuations do not exceed a few per cent over relatively short periods, and are, therefore, of very little relevance to thehydrologist who is generally confronted with dissolved carbon from avariable vegetation covering along and uncertain period of time. Thestrong increase in theatmospheric 14C level due to thenuclear test explosions is of more relevance to thehydrologist. During thebomb explosions 14C (and 3H) is being produced by thesame nuclear reactions that are responsible for thenatural production. In thenorthern hemisphere thepeak concentration occurred during thespring of 1963, when it was about double thenatural concentration (Fig.8.3). In thesouthern hemisphere amore gradual increase has taken place. This is due to thefact that theseasonal injections of 14C from thestratosphere into thetroposphere primarily occurred over thenorthern hemisphere, while air is not easily and simply transported across theequator. The14C increase only gradually leaked through theequatorial regions to thesouthern troposphere. 8.1.3.2. Vegetation and soils Thehigher 14C levels have entered thesoil vegetation, and have become detectable in theCO2gas, present in thesoil and playing amajor role in theformation of dissolved inorganic carbon in groundwater. In this way thebomb effect possibly increases the14C content of young groundwater. TheCO2generated in thesoil by decaying plant remains and by root respiration is relatively young and therefore contains about theatmospheric 14C concentration (14a=100%) (Fig.8.3). 8.1.3.3. Seawater and marine carbonate Because seawater is in constant exchange with atmospheric CO2, one would expect that, like thestable carbon isotopes, that an isotopic equilibrium exists between thetwo reservoirs. This is not thecase, due to thephenomenon of upwelling of water from greater depth and aconsiderable age. This may extent to ages of 1500 years, equivalent to an 14a value of theorder of 85%. In general, in surface seawater 14C contents are observed in therange of 95%. 78

1200 1000 800 600 400 200 0 1960 60

northern hemis phere

14

southern hemisphere

65
14

1970 70

75

1980 80

85

90

1990 95

C content of atmospheric CO 2

Fig. 8.3. Curve representing thenatural 14C content of atmospheric CO2 (data for Nordkapp, Norway, representative for the northern hemisphere) (Nydal, pers.comm.). Test explosions of nuclear weapons since thefifties and especially theearly sixties have temporarily increased the concentration by a factor of two. Due to isotopic exchange with the oceans, 14 C is slowly returning to normal. The influence on the southern hemisphere was obviously smaller. The seasonal variation of some per cent during thelate 1960s has been smoothed out, since they are not relevant in hydrology, contrary to the 3H variations to be discussed later in this chapte

8.1.3.4. Groundwater By processes of erosion and re-sedimentation fossil carbonate is generally part of terrestrial soils. Here it may be dissolved by theaction of soil-CO2, which is contained by the infiltrating rain water. In this way thedissolved inorganic carbon in groundwater also contains 14C [17]. As thecarbonate is very old and thus without 14 C (14a=0%) generally, but not always (see Volume 4 on Groundwater) thebicarbonate resulting from thereaction: CO2 + H2O + CaCO3 Ca2+ + 2HCO! (8.9)

will have a14C content one half that of theCO2 (14a=50%) (cf. 13C, Fig.7.7). Isotopic exchange with soil CO2 or atmospheric CO2 lead to higher 14 C concentrations of theinorganic carbon fraction of recent groundwater, in combination with respectively decreased or increased 13 (see Sect. 7.2). Theincreased level of 14C in atmospheric CO2 since 1963 can lead to 14C contents in soil organic matter and soil CO2, which even exceed thenatural atmospheric value.

NATURAL ABUNDANCE OF RADIOACTIVE ISOTOPES of C and H

8.1.4.

14

C age determination

14 Knowing therate of radioactive decay ( or T1/2), Astandard theage (T=time elapsed since death) of acarbo14 0 14 A Asample T /2 5568 be calsample naceous sample, (8.10) T = 1organic ln 14 or inorganic, = canln = 8033 ln 14 asample 14 14 0 14 ln 2 Astandard .693 a, if theA C culated from themeasured activity, 0 standard activity at thetime of death, 14ainitial , is known (Eq.6.7): In order to avoid confusion, theoriginal (conventional) half-life of T1/2=5568 years is still T = (T1/2/ln2)(14a/14ainitial) 14 for geobeing used international agreement Theresult isby called theconventional C age BP logical and archaeological dating. In hydrolof thesample, that is theage Before Present (by Considering this equation, 3 quantities have to ogy, however, we will apply thetrue half-life definition: before AD1950). 14 i be well established: T1/2, a and theproper valof 5730 years. ue 14a of the14C activity of thesample. As was explained before, thecondition that sample and Thepractice using these conventional ages is neat reference activity are determined at thesame time but of course a simplification. Apart from using thewrong half-life, theassumption of aconstant and under similar conditions results in the14a val14 C content of living organic matter is proven unue valid for theyear 1950, i.e. theage obtained true. However, by applying the14C calibration counts back from 1950. curve, i.e. theempirical relation between theconBy international convention: ventional age of tree rings (to 10000 years BC) and their real age, both problems are solved and (1) theinitial activity equals thestandard activ14 C ages are translated into real ages (Fig.8.5). ity in AD1950; Thewiggles of thecalibration curve are due (2) the 14C activities have to be normalised for to thenatural variations in theatmospheric 14C fractionation (samples to 13=25, Ox1 content, mentioned in Sect.8.1.3. Further details to 19, Ox2 to 25) (see Chapter 10); about radiocarbon dating are, for instance, given by [82, 83] (3) theoriginal (Libby) half-life of 5568 has to be used.

T T = 1/ 2 ln ln 2

14

Asample

14 0 A 5568 sample = ln 14 0 = 8033 ln 14 asample Astandard 0.693

This results in therelation:

atmosph. CO2 105%

exchange

precipitation

plants / humus 100% oceanic HCO 3 100% humus CO 2 100%

soil H 2O

dissolved CO 2 100% soil CaCO 3 0%

groundwater 50% HCO 3

marine CaCO 3 100%

erosion / sedimentation

groundwater 6585% DIC

Fig. 8.4. Schematic representation of theformation of dissolved inorganic carbon in groundwater. Thepercentages are the14a values indicative for thecarbonate dissolution, which is themost relevant process in most types 14 of groundwater. The 14a value of groundwater HCO 3 of 50% results in higher values of a in thetotal dissolved carbon because of theadditional CO2 and of isotopic exchange with thesoil-CO2.

79

INTRODUCTION

8.1.5.

Dating groundwater
14 i N ()

350 300 250 200 150 100 50 0 -50 -14000

real age in years BC/AD

Dating water as such has no meaning. Dating groundwater is determining theage of groundwater, i.e. thetime elapsed since thewater became groundwater, in other words, since it infiltrated into thesoil as precipitation or any other type of surface water (rivers, lakes). In principle there are some methods of calculating or estimating groundwater ages, for instance, based on hydrodynamical modelling. Here we discuss theapplication of radioactive decay. Essential to know is theinput function, i.e. the(time dependent) amount of radioactive tracer that infiltrated. Thewater molecule itself has one radioactive isotope, tritium or 3H. Thedisadvantages are that both theactivity and thehalf-life are very small. Possible applications will be discussed in Sect.8.3. Therefore, we are driven back on radioactive compounds dissolved in thewater, rather than thewater itself. In Chapter 12 we will discuss several radioactive isotopes that can be applied. Here we are concerned with 14C, which has avery attractive half-life for solving hydrological problems. It is contained by dissolved inorganic carbon (DIC) as well as dissolved organic molecules (DOC). 8.1.5.1. Dating groundwater with DIC If 14ai were known and if no carbon entered or escaped thegroundwater in thecourse of time, thewater age (since infiltration) would be given by: T = 8267 ln [(14a / 14a0standard) / (14ai / 14a0standard)] = 8267 ln(14a / 14ai) (8.1 we have to warn thereader that, for geochemi14 reasons, to trustworthy groundwaItcal is tempting to obtain apply this C method to DIC: ter ages by applying theradiocarbon dating thesampling and measuring techniques are relatechnique toand DIC is by no means simple and tively simple available. However, straightforward. Volume 4 of this series will discuss thevarious problems. Here we limit ourselves with abrief review. Theinitial 14C activity 14ainitial (=14ai) in thetotal dissolved inorganic carbon content (DIC) of infiltrating groundwater can not simply be taken as being equal to 14astandard, as in theprocedure of calculating conventional ages (Eq.8.9). Estimating theoriginal, real value 14ai or 14ai of recent groundwater is more complicated. 80

-12000

-10000

-8000

-6000

-4000

-2000

2000

14000
C age in years BP Conventional

12000 10000 8000 6000 4000 2000 0 -14000

14

-12000

-10000

-8000

-6000

-4000

-2000
BC

0
AD

2000

Real age in years AD/BC

Fig. 8.5. Variations in the14C content of atmospheric CO2 in the past (upper curve), resulting from 14C measurements of treerings of accurately known age by anumber of laboratories, and of annual growthrings in corals [80]. Theparameter showing thedeviations from the standard is defined by Eq.11.47. The data result in thecalibration curve (lower curve), used for translating conventional 14C ages into real ages [81] (Sect.11.5.4.3). The straight line in the calibration curve represents y=x.

8.1.5.1.1. Theorigin of 14C in DIC In general, theformation of DIC in groundwater essentially consists of two processes: (i) thedissolution of carbonate by H+ in H2CO3 from atmospheric CO2 (in arid regions) or soil CO2, or in organic acids, and (ii) isotopic exchange with 8.1.3. Various modCO2 as mentioned in Sect. els are dealing with thedevelopment of DIC and theconcurrent 13 and 14a values. 8.1.5.1.2. Thechemical/isotopic mass balance TheCO2-CaCO3 concept first proposed by [17] is based on themass balance of inorganic carbon (Fig.8.4) in theclosed system of soil CO2, soil CaCO3 and water. CaCO3 is dissolved by an equal molar amount of biogenic CO2 (0.5b), whereas an additional amount of CO2 (a) is required to stabilise thesolution chemically. For the14C analysis of ground water all CO2 is extracted from thesolution after acidification. Rewriting Eq.8.9 in amore complete form gives:

8.1.5.1.2

Les balances de masse chimique/isotopique

g l

a+b

Le concept CO2CaCO3 propos initialement par Mnnich (1975) est bas sur le bilan de avec les expressions respectives de 14ai et 13 en lieu et place de a masse du carbone inorganique (Fig. 8.4) dans un systme clos vis--vis du CO2 du des sol, valeurs du Numriquement, avec lutilisation des valeurs de 13 et 14a des Figs. 7.7.et 8. CaCO3 du sol et de leau. Le CaCO par une part molaire quivalente de CO 3 est dissous NATURAL ABUNDANCE OF RADIOACTIVE ISOTOPES of C and H2 les eaux souterraines conduit des valeurs 13 et 20% de COncessaire 2 dissous dans biognique (0,5b), tandis que un taux additionnel dede CO ) est pour stabiliser 2 (a et eaux 60%, souterraines, respectivement. chimiquement la solution. Pour lanalyse du 14C des tous les CO2 sont 8.1.5.1.3. Isotopic exchange in an open system (a +0.5b)CO2 + 0.5b CaCO3 + H2O 0.5b Ca2+ extraits de la solution La r-criture de lEq. 8.9 sous une forme plus (8.12) +b HCO! +aprs a COacidification. 2 13 In an open system the and 14a values may fur8.1.5.1.3 Echange isotopique en systme ouvert complexe donne: where aand b are therespective concentrations ther change by isotopic exchange of DIC thus 13 14 of dissolved carbon dioxide and bicarbonate. In systme Dans2+ un valeurs de CO 2et a peuvent dans le tem , which may voluer be formed with les surrounding ouvert, + 0,5 b CaCO + H O 0,5 b Ca + b HCO + a CO (8.12) ( a +0,5 b )CO 2 3 2 3 2 this simple concept thechemical composition in theunsaturatsoilas well as atmospheric CO isotopique du DIC ainsi form et le CO22 environnant qui peut tre du C of thewater, in casu thecarbonic acid fractions, ed dans zone. principle both values change par- changent en pa atmosphrique laIn zone non sature. En principe, lesin valeurs 14 ou a et b sont les concentrations respectives de themixture dioxyde de carbone dissous et de bicarbonate. a value of of determine theoriginal allel to an isotopic equilibrium situation between situation dquilibre isotopique entre le DIC et le CO2, de telle faon que les v HCO! : composition chimique de CO2 and that the14a and 13 values are DIC and theCO Dans ce contexte simple, la leau cest--dire les fractions 2, sodacide 13 par: 14soient couples coupled by: carbonique, permettent de dterminer la valeur originelle a du mlange entre CO2 et HCO3 : (8.13) (a + b)14a = 0.5b 14al + (a + 0.5b)14ag 14 aex 14 a0 13 ex 13 0 14 14 14to thesolid car= (8.17) where thesubscripts l and g refer 14 (a + b) a = 0,5b al + (a + 0,5b) ag aeq 14 a0 13 eq(8.13) 13 0 bonate and thegaseous CO2, respectively. As in most groundwaters, pH is low so that theonly carwhere ex, eq 0 respectively o les ex, thesubscripts eq et 0 se rfrent, respectivement, rela valeur actuelle gazindices respectivement. Comme pour la and o les indices l et g se rfrent au carbonate solide et CO ) and bonic acid fractions are thedissolved CO2 (a2 fer to theactual values after isotopic exchange, 14 est faible, les fractions lultime valeur quand lquilibre isotopique avec le CO2 environna plupart des HCO eaux ! souterraines le pH dacide carbonique correspondent a values given in isotopique, Fig.8.4 (b). With the 14 theultimate values when isotopic equilibrium 14 valeurs la dissolution en systme ferm. La combinaison de l C aoriginale thedissolved is expected to les have avaleur seulement aux CO2 (a) et bicarbonate HCO3 (b) dissous. Avec donnes aprs dans la Fig. 8.4, le with thesurrounding CO2 has been reached and 14 of content of 50%, while an additional amount dilution isotopique et desquune corrections dchange ont t utilises par de nom C de 50%, tandis partie bicarbonate dissous est suppos avoir une teneur en theoriginal values after closed-system dissoloushifts the 14C content of CO2 (with 14a=100%) 14 14 (Gonfiantini, 1971; Mook, 1976; 1980; Fontes et Garnier, 1979). Toutefois, additionnelle du CO2 (avec a = 100%) dplace la teneur en C tion, du DIC (= a + b ) vers une respectively. Thecombination of theisotoDIC (=a+ b) to asomewhat higher value. This 14 chimiques et gochimiques en milieu souterrain sont si correccompliques que les mo pic dilution correction and theexchange valeur quelque peu plus leve. Cette mthode 14 destimation de la teneur en C originelle des C content of method of estimating theoriginal 14 i tion have been used by several authors [8790]. constituent approches raisonnables eaux souterraines, et donc and de correction de lgetheapparent apparent de par des le fait que a 100%, est mais ne peuvent pas tre considr groundwater, thus correcting However, thechemical and geochemical con14 ii a 100% is referrred to as age for thefact that mthodes de corrections prcises. appele la correction de dilution chimique (Ingerson et Pearson, 1964; Geyh et Wendt, 1965). ditions underground are so complicated that thela chemical dilutionen correction [84, With 14 teneur originale C du DIC est: 85]. Avec 14al = 0% theabove models may be 14 14 Sous climat tempr avec des sols reasonable couvertureapproaches vgtale, les valeurs de 1 al =0% theoriginal C content of theDIC is: butgnralement are not to be considered clean correction meth11 14 et 65 85%, respe observes sont dans la gamme de a + 0.5b 14 a + 0.5b ods. 14 i a = ag = 100% (8.14) a+b a+b (8.14) In temperate climates where theland has aveg14 i 14 etation cover, theobserved values of 13DIC and Thefactor / ag = 14ai/14a0 is called thedilution 14 i 14 14 i a 14 14 valeur comprise entre 0,5 Le facteur factor a / agwith = a / a0 est nomm0.5 facteur de dilution avec une aDIC are generally in therange of 11 to 14 avalue between and 1. and 65 to 85%, respectively. et 1. An alternative approach is to consider thestable carbon isotopic composition of DIC in theground8.1.5.2. Dating groundwater with DOC water, instead of thechemical composition. For 136 13 C asimilar mass balance can be written as for 14C Attempts were made to determine theage of in Eq.8.13: groundwater, i.e. the time elapsed since infiltration, by means of dating thedissolved organic (a + b)13DIC = 0.5b 13l + (a + 0.5b)13g (8.15) carbon (DOC) content of thewater sample. Based on their solubilities in specific acid solutions, where thesubscripts are thesame as in Eq.8.13. thesoluble and thus mobile organic compounds Theisotopic and thechemical dilution correction are subdivided in fulvic acids (soluble at low pH) are now related by [86]: and humic acids. These organic molecules, origi13 DIC 13 l a + 0.5b nating from thedecomposition of organic matter, (8.16) (8.16) = 13 are relatively resistent against further degrada g 13 l a+b tion. with therespective expression for 14ai and 13 val14 i 13 Alsoof here a and Numerically, values instead a we andare b confronted (Eq.8.14). with theproblem to with the respective expression ues instead of aand for b (Eq.8.14). 14 i a values to therecently infiltrated water. assign 13 14 and aavalues 7.7 and 8.4 8.4 a 20% fraction of dissolved using the and 14 values of of Figs Figs.7.7.and CO2 Numerically, using the 13 [91] concluded that only thefulvic fraction origia20% fraction CO2 in groundwater 13 of dissolved 14 i a values of 14.6 and 60%, nates respectively. in groundwater results13in and with certainty in thesoil zone and thus is 14 i results in and a values of 14.6 and 60%, 14 C ages, based on an 14ai able to produce reliable respectively. value in therange of 85 10%. This range of val8.1.5.1.3 Isotopic exchange in an open system ues depends on theaverage age of thesoil organic In an open system the 13 and 14a values may further change by isotopic exchange of DIC thus formed with surrounding CO2, which may be soil- as well as atmospheric CO2 in the 81 unsaturated zone. In principle both values change in parallel to an isotopic equilibrium situation

between DIC and the CO2, so that the 14a and 13 values are coupled by:

INTRODUCTION

matter in therecharge zone, which can be hundreds of years. 8.2. Relation between C and C variations
13 14

8.3.2.

Reporting 3H activities and the3H standard

Asurvey of therelevant values of the14C (14a in %) and 13C content (13 in ) in thereservoirs relevant for thehydrological cycle is given in Fig.8.6. Thevalues are merely indicative and do not exclude deviations. The figure is a combination of theabove discussions represented schematically in theFigs.7.5, 7.7 and 8.4. Special attention in this figure needs the value for marine carbonate. Accidentally theobserved 14 a values for vegetation and marine carbonate are almost equal. Thefact is that two processes cancel each other: (i) starting with organic matter on land with 13 about 25 and 14a=100% (by definition, cf. Sect.7.1.2), the difference in 13 between land vegetation and marine carbonate (via atmospheric CO2) of about 25 requires 14 a of thelatter to be 5% (=225) larger; (ii) theupwelling of deep sea water with ages of up to 1500 years generally causes thesurface ocean water to be depleted by (accidentally) also 5%. 8.3. Theradioactive hydrogen isotope 8.3.1. Origin of 3H, decay and halflife

Because thenuclear reaction (Eq. 8.18) has alower probability than reaction (Eq.8.1) and because theresidence time of 3H in theatmosphere is much smaller than that of 14C, thenatural 3H concentration in theair is much smaller than that of 14C. Natural 3H abundances are either presented as specific activities in Bq per litre of water) or in Tritium Units (TU), thelatter by definition equivalent to aconcentration of 3H/1H=1018 (1 TU=3.19 pCi/L=0.118 Bq/L) (Sect. 4.3). For 3H, as for 14C, it is extremely difficult to determine the absolute specific activities. Tritium activities, are therefore related to areference water sample which is measured under equal conditions. For this purpose theIAEA and NIST (theformer NBS) has available atritium standard NBS-SRM 4361 of 11100 TU as of September 3, 1978 [92]. After being related to this standard, 3H concentrations are reported in absolute values (3A in TU), corrected for decay to thedate of sample collection. 8.3.3. Survey of natural 3H variations

Under undisturbed natural conditions the3H concentration in precipitation was probably about 5 TU, which is equivalent to aspecific activity of about 0.6 Bq/L [94]. Following thenuclear weapon tests of theearly sixties, the3H content of precipitation temporarily increased by a1000-fold in thenorthern hemisphere (Fig. 8.8). Since 1963 this extreme 3H content has decreased to essentially natural values in winter and about twice natural in summer. Alarge part of the3H (as well as 14C) produced by thenuclear explosions has been injected into thestratosphere and returns to thetroposphere each year during spring and early summer. This causes theseasonal variation in both 3H and 14C, more pronounced in theformer, because theresidence time of H2O to which 3H is coupled in theatmosphere is very small ( in theorder of weeks). Theprobability of contamination of young groundwater by bomb 3H prevents thewater to be simply dated by measuring thedegree of 3H decay. Nevertheless, 3H data can often be used to determine dates ante quem or post quem. For in-

Theradioactive isotope of hydrogen, 3H (tritium or T), originates (as does 14C) from anuclear reaction between atmospheric nitrogen and thermal neutrons [74]:
14

N + n 12C + 3H (8.18)

The 3H thus formed enters thehydrologic cycle after oxidation to 1H3HO (Fig.8.7). It finally decays according to: H 3He + (8.19) According to arecent re-evaluation [93], amore preferable is 4500 8 12 days keV value and ahalf-life of 430 with Emax=18 (equivalent to 12.32 year; theformer value has years [92] (Fig.8.2). been used in this text).
3

82

NATURAL ABUNDANCE OF RADIOACTIVE ISOTOPES of C and H

stance, water with 3A < 5 TU must have amean residence time of more than 40 years; water having 3A > 20 TU must date from after 1961. Thetracer use of 3H will further be discussed in theVolume 4 of this series. 8.4. Comparison of 3H and 14C variations 8.4.1. Relation between 3H and 14C in theatmosphere

over time of water in theatmosphere from evaporation of ocean water to precipitation very short (in theorder of weeks), while theexchange of CO2 between theatmosphere and ocean water is very slow (in theorder of years). (3) For thesame reason does 14C show much smaller seasonal amplitudes than 3H; theconsequence for thelatter is that in temperate climates, where the main infiltration of rain occurs during thewinter half-year, groundwater rarely shows thehigh 3H values observed in precipitation during theearly 1960s. (4) The 14C increase after 1960 in theair over thesouthern hemisphere is less pronounced than over thenorthern hemisphere, as themajority of thenuclear tests took place in thenorth and, moreover, since theair is not easily transported across theequator; for 3 H theconsequences are that theequivalent curve for theSouthern hemisphere is much different: it is less regular, shows amaximum at 30 TU around 19631965 with oc-

At first we will compare the curves showing the14C and 3H variations in atmospheric CO2 and H2O, respectively (Figs 8.3 and 8.8), because they give important information on theglobal carbon and water cycle, respectively. Themain differences are thefollowing. (1) Theeffect of thenuclear bomb 14C and 3H had amuch more pronounced effect on theatmospheric content of thelatter, because thenatural 3H concentration is so much lower. (2) Therestoration to natural conditions goes faster for 3H than for 14C, because theturn-

HCO 3 in isotopic equilibrium vegetation/soil 100 80

14

air CO 2 apparent

CaCO 3

a (%)

exchange with air CO 2 as surface water

60 ageing 40 ageing groundwater ageing

20
0 fossil fuels 32 28 24 20 16 12
13

fossil carbonate 8 4 0 +4

()

Fig. 8.6. Schematic representation of the relation between variations in 13C and 14C in nature. The groundwater values have been explained in the Figs 7.7 and 8.5. The marine bicarbonate and solid carbonate (vertically dashed) values for thecase of an isotopic equilibrium with atmospheric CO2 are not observed in theocean. Theupwelling of deep, relatively old (1500 a) water causes thesurface water to be lightly depleted in 14C. Theapparent age of this water and consequently of themarine carbonate formed in this water (horizontally dashed) is about 400 years (equivalent to 5% 14C).

83

Isotopes radioactifs de lHydrogne et du Carbone

INTRODUCTION

of theoccurrence of 14C and 3H in groundwater 8270=(ln2)/ years. aqualita- des conclusions o 8270 = where (ln2)/T1/2 ans. DunT1/2 point de From vue qualitatif, may not lead to theidea that, using these isotive point of view, approximate conclusions approximatives peuvent tre afew rendues partir des donnes isotopiques. P topes, we are able to simply measure the age of 3 can be drawn from isotopic data. For instance, if 1 UT), lchantillon deau montre une activit H mesurable (suprieure groundwater, i.e. theperiod of time elapsed since thewater sample shows ameasurable 3H activity theinfiltration of thewater. rcente, i.e. infrieure 50 ans, ou correspond un mlange deaux rcente (larger than 1 TU), thewater is subrecent, i.e. less enfin, contient ajout old, dun pourcentage rcente. Avec de Themain obstacle is theunknown isotopic values than un 50 years or certain is amixture of young deau and old 14 3 3 H as at time zero, themoment of infiltration, for mesurables en C H, leau est an certainement de plusieurs dizain water, oret at least contains admixture ge of acer14 cerwell as for 14C. However, 14C and 3H together C doit tre proche ou sup dannes. Si leau est trs rcente, lawater. teneurWith en no tain percentage of recent measurtainly offer thepossibility to set limits to absolute 14 3 14 C and H thewater is certainly afew tens of able parce que le CO2 du sol contient probablement du C thermonuclaire. ages, especially in combination with hydrogeothousands of years old. If thewater is very recent, logical and hydrochemical evidence. Le volume 4 de14 cette srie est tout particulirement dvolu a ces problmes et ( C content is expected to be close to or above the then is likely con100%, because Determining relative ages (i.e. theageUne differsynthse simplifie et thesoilCO gnrale est2 donne sur la to Fig. 8.9. Avec les eaux 14 tain bomb C. ences between neighbouring samples, which is nous refrons aux eaux qui se sont infiltres depuis quelques dizaines dan souterraines jeunes peuvent avoir nimporte quel ge compt en centaines da souterraines anciennes en plusieurs milliers dannes. Enfin, le terme trs a galement aux eaux souterraines fossiles qui ne contiennent plus de 3H et 14C e 3 H 3H 3H plusieurs dizaines de milliers dannes. Les eaux qui ont des teneurs relativem 3 3 H H 3 H et plus faibles en 14C que les eaux rcentes sont probablement des mlange 14 3 N + n 12C + 3H H 3He + 3 H et anciennes.
3

Le principal obstacle est la valeur isotopique inconnue au temps zro, linfiltration, pour le 3H aussi bien que pour le 14C. Toutefois, le 14C et le casional peaks up to 80 TU, and aslow de-de faon oftensure equally relevant) less des complicated, offrent la possibilit de is mettre limites auxat ges absolus, en p crease to thenatural level (5 TU) at present. least if thechemistry does not point to theaction les combine avec des preuves hydrogologiques et hydrochimiques. of processes underground such as carbonate 14 (5) C is being used to calibrate global carbon Dterminer des ges relatifs (i.e. les diffrences dges dissolution, decomposition of additional (old) entre or- des chantillo cycle models, indicating theexchange (and ganic matter, and certainly if we are dealing with moins compliqu, au moins si la chimie montre labsence de processus soute transition) time of (additional) CO2 between 3 a mixture of different water that could influ air and sea; H is being applied in oceanogla dissolution de carbonates, la dcomposition de matire organique (ancienn ence thecarbon isotopic composition. In that case raphy, indicating therate of vertical water certaine de mlanges deaux diffrentes- qui pourraient influencer la composi theage difference between water samples colmovement and lateral water flow. du carbone. Dans ce cas, la diffrence dges entre des chantillons deaux p lected at two geographical locations k and k+1 is endroits gographiques k et k+1 sexprime ainsi: expressed as: 8.4.2. Relation between 3H and 14C 14 a in groundwater (8.20) T = 8270 ln 14 k +1 a k We have already emphasised that our discussion

hy drol og ical

c y c l e

H 1HO

precipitation evaporation

surface runo

oceans

i nfil tra ti on hy dr ol ogic al c y c l e

rivers

Fig. 8.7. Origin and distribution of 3H in nature. Contrary to 14C, theturnover of 3H is very fast, except where it is fixed in glacier ice or groundwater.

84

NATURAL ABUNDANCE OF RADIOACTIVE ISOTOPES of C and H

4000
northern hemisphere

H concentration (TU)

3000

2000

1000

0 1955

1960

1965

1970

1975

1980

1985

1990

Fig. 8.8. Smoothed curve representing the average 3H content of precipitation over the continental surface of theNorthern hemisphere.

Volume 4 of this series is especially devoted to these problems and (im)possibilities. A general and simplified survey is shown in Fig.8.9. With recent groundwater we refer to water that infiltrated not more than some tens of years ago. Young groundwater may have any age of hundreds of years, old groundwater thousends. Finally very old, also referred to as fossil groundwater does not contain 3H and 14C and is several tens of thousands of years old. Waters which are relatively high in 3H and lower in 14C than recent water are likely to be mixtures of young and old water.

100

75 A (TU)

mixed

50

recent groundwater

waters

25

fossil

old groundwater

young

25

14

50 a (%)

75

100

Fig. 8.9. Schematic representation of relations between the14C and 3H content in groundwater. The scheme is merely indicative and serves to give ageneral impression. Theterminology is discussed in thetext.

85

9. CHEMISTRY OF CARBONIC ACID IN WATER

9.1. Introduction Studying thecarbon isotopic composition of water, whether it concerns freshwater or seawater, acomplication arises from thefact that thedissolved inorganic carbon always consists of more than one compound, while also thepresence of gaseous CO2 and solid calcium carbonate may be relevant. In fact we are dealing with thefollowing compounds and concentrations: gaseous CO2 (occasionally denoted by CO2g) with apartial pressure PCO2 dissolved CO2 (denoted by CO2aq) dissolved carbonic acid, H2CO3 with a = [H2CO3] + [CO2aq] balance has to be taken into account. In this chapter some examples are given. (b) Measuring thecarbon isotopic composition of asolution comes to extracting thetotal CO2 from thesample after acidification, instead of single compounds. For theessential translation of 13 of total dissolved carbon to 13 of single compounds, and conversely, theinorganic carbon chemistry, i.e. of thedissolved inorganic carbon is required.

dissolved bicarbonate, HCO! with 2 13 9]) RDIC = + [CO 3 ([CO 2 aq] + [H 2CO 3 ] + [HCO3 ]Chapitre b=[HCO!] Chapitre 9 2 13 13 13 13 2 13 =][CO ] RCO2 + [H CO ] + [HCO 3 ] RHCO3 + [CO 3 ] [CO aq ] + [H CO ] + [HCO ] + [CO R = ( ) aq R 2 aq 2 3 H CO DIC 2 2 3 3 3 2 2 3 2 3 3 dissolved carbonate, CO$ with c=[CO$] (9.1) 13 2 13 13 13 13 2 CO [CO ( = [CO 2 aq] RCO2aq + [H 2 CO 3 ] RH 2CO + [HCO ] 2R + [HCO [CO 3 3 ]] + R 2 ]) 13 RDIC = 2 aq ] +3[H 3]+ (9.1) HCO CO 3 3 3 3 [CO [H + [CO = ([CO total dissolved inorganic carbon, DIC, ou, with 3 ]) R DIC 2 aq ] +13 2 CO 3 ] + [HCO 3 ] 2 13 e 13 composs 13 en = insrant les symboles des divers mentionns prcdemment [CO 2 aq] 13 RCO2aq + [H 2 CO 3 ] 13 RH 2CO3 + [HCO 3 2 ] 13 RCO ] 13 RHCO3 + [CO 3 CT=a+ b + c = [CO aq ] R + [H CO ] R + [HCO ] R + [CO ] R or, inserting thepreviously mentioned symbols aq et en acide H CO tant fra concentrations 2 en CO2 CO aq 2 3 carbonique, H 2CO 3 3, ce dernier HCO3 3 une CO 2 3 2 ou, en insrant les symboles des divers composs mentionns prcdemment et en combinant les solid carbonate, CaCO3 (occasionally denotfor thevarious concentrations and combining donc ngligeable, la composition isotopique du carbone total dissous ( C = a + b + T carbonique, H2CO ce dernierdes tant une fraction trs petite et prcdemment et en en CO2aq et en acide ou, en insrant les mentionns 3, symboles ed concentrations by s) and thecarbonic acid, theconcentration of divers CO2aqcomposs ou, en insrant les symboles des divers composs mentionns prcdemment et en donc ngligeable, la composition isotopique du carbone total dissous (C b + c) est : H2CO aq et en acide carbonique, tant une fracti concentrations en CO T=a+ 2 3, ce dernier CO , thelatter being anegligibly small fracH 2 3 et aen acide H2CO3, ce dernier tant une fracti concentrations en cRc + bR Theambiguity in using carbon isotopes now con13 CO2aqaR b + carbonique, R = donc ngligeable, la composition isotopique du carbone total dissous ( C tion, theisotopic composition of thetotal dis- T = a + b + c) e CT T sists of two observations: aR + bR + cRdonc ngligeable, la composition isotopique du carbone total dissous (CT = a + b + c) e C T 13 b c solved carbon (CT=a+ b + c) is: (9.2) RCT = a (1) On theone hand, only theisotopic composiCT aRa + bRb + cRc 13 = insrant aRa + bR cRc de fractionnement propres tels que mentionn 13 RCT en etthat inversement, les + facteurs tion of asingle compound in relation to RCT = CTb (9.2) C ofetanother compound is les geochemically or inversement, en insrant facteurs de fractionnement propres telsTque mentionns avant: 13 hydrologically meaningful. We have seen an CT inserting RCT 13 conversely, and fractionation T et inversement, en insrant les facteurs de theproper fractionnement propres tels que mentionns = b R example of this statement while discussing b et inversement, en insrant les + facteurs de fractionnement propres tels que mentionns 13 factors as mentioned before: + a b c C R a / b c / b T CT of ground13 thecarbon isotopic b (9.3) Rb = composition 14 b + c CT 13 RCT aas (Figs water, for 13C as well 13 a / b +C c / b 7.7 and CT 13 Rseront = R b (9.3) CT 13 b Les paragraphes suivants consacrs lanalyse de la composition 8.4). In other words: an isotopic fractionRb = a a / b + b + c c/b b + + a b c carbonates. a / b la composition c/b ation is afundamental, physico/chemLes factor paragraphes suivants seront consacrs lanalyse de chimiques deaux Thenext sections will be devoted to analysing ical quantity only if it is theratio between carbonates. Les paragraphes suivants seront consacrs lanalyse de la composition ch Les For paragraphes suivants composition seront consacrs lanalyse de la composition ch thechemical of carbonate waters. two isotopic ratios of single compounds. carbonates. 9.2 LES EQUILIBRES DE LACIDE CARBONIQUE instance: carbonates.

Once thevarious concentrations of thedissolved Chapitre 9 species, to be deduced in thenext sections are known, the13C mass balance: Chapitre 9

(2)

9.2 LES DE LACIDE CARBONIQUE En prsence de CO2 gaz, le CO2 dissous change avec le EQUILIBRES CO2 gaz: 9.2 LES EQUILIBRES DE LACIDE CARBONIQUE In CO thepresence ofCO gaseous CO 2(g) + H2O 2(aq) + H 2O2, dissolved CO2 En prsence de CO gaz, le CO dissous change avec le CO2 gaz: 2 2 exchanges with 2gas:change avec le CO2 gaz: En prsence CO2 gaz, le COCO (a) On theother hand, mass balance con- de 2 dissous CO2(g) + Hin (9.4) 2O CO2(aq) + H2O

9.2 LES EQUILIBRES DE LACIDE CARBONIQUE de CO2 gaz, le CO2 dissous change avec le CO2 gaz: a/b = 13Ra/13Rband13c/b = 13Rc/13Rbb En prsence 9.2. Carbonic acid equilibria

siderations thecarbon isotopic composi- COCO 2H 2(aq) 2OCO 2CO + H2+ OH (aq) +3H2O 2(g) CO 2(g) + H2O CO2(aq) + H2O (9.4) tion of amixture of compounds is rel- CO 2(g) + H2O CO2(aq) + H2O H2CO (9.5) CO 2(aq) + H2O 3 evant. For instance, if CO 2 or CaCO ou g 3 et aq se rfrent phases gaz et dissoutes respectivement. Bien que l + H2aux O H2CO CO 2(aq) 3 (9.5) CO2(aq) + H2O H2CO3 are being removed from adissolved car- soit 3 largement suprieure celle H2CO3 dissous CO 2(aq) CO2 (aq) + H2O HBien 2CO3 oubon g etsolution, aq se rfrent aux phases gaz et dissoutes respectivement. que la de concentration en (dun facteur de 10 where g and aq refer to thegaseous and dissolved of for estuarine mixing of 3 concentration de tous les CO par [H2CO d quilibre e 2 dissous 3]. La condition CO suprieure celle dissous (dun facteur de 10 ), nous noterons la ou gde et H aq se aux phases gaz et dissoutes respectivement. Bien que la c 2(aq) soit 2CO 3 rfrent C mass phase, respectively. Although theconcentration freshandlargement seawater, thetotal 13

ou quantifie g et aq se rfrent aux phases gaz et dissoutes respectivement. Bien que la c de Henry) : par la solubilit molaire Ko (Loi concentration de tous les CO2 dissous par [Hsoit ]. La condition d quilibre entre les 3 phases CO largement suprieure celle de H2CO dissousest (dun facteur de 103 ), n 2CO3 2(aq) CO2(aq) soit largement suprieure celle de H2CO3 dissous (dun facteur de 103), n de Henry) : quantifie par la solubilit molaire Ko (Loi concentration de tous les CO2 dissous par [H2CO3]. La condition d quilibre entr concentration de tous[H les CO 2 CO 32] dissous par [H2CO3]. La condition d quilibre entr quantifie par la K solubilit molaire Ko (Loi de Henry) : o = quantifie par la solubilit molaire Ko (Loi de Henry) : PCO [H 2 CO 3 ] 2 2 Ko = (9.6)

PCO2

Ko = [H 2 COdu ] ou la pression partielle K = P 3 CO2 atmosphrique PCO2, est exprime en atm, Ko est l

[H 2 CO 3 ]

En prsence de CO2 gaz, le CO2 dissous change avec le CO2 gaz: CO2(g) + H2O CO2(aq) + H2O CO2(aq) + H2O H2CO3
INTRODUCTION

(9.4) (9.5)

farphases exceeds of dissolved H2CO3 Bien of rfrent CO2(aq) AT = [HCO + 2[CO$] +en [OH] [H+] + [other ou g et aq se aux gazthat et dissoutes respectivement. que la !] concentration 3 3 denote theconcentration theorder of 10 ) we weak anions] (9.14) CO2(aq) soit (in largement suprieure celle de H2 CO3 dissous (dun facteur deacid 10 ), nous noterons la by [H CO ]. Theequilibrium of all dissolved CO 2 2 [H 32CO3]. La condition d quilibre entre les phases est concentration de tous les CO2 dissous par in which concentrations of other weak acids may condition between the phases is quantified by (Loi de Henry) : quantifie par la solubilit molaire K be included in theinterest of high precision, such o themolar solubility Ko (Henrys law):
Ko =

et et

Under natural conditions [H+] and [OH-] are negligibly small compared to thecarbonate species where theatmospheric CO2 partial PCO2en , atm, PCO2pressure, , est exprime Ko est la solubilit molaire ou la pression partielle du CO2 atmosphrique concentrations. Thesum of theweak acid and 1 1 is thesolubility in mol L atm is in atm, K 1 1 o alkali-ion en mol L atm , et [H2CO3] est la concentration en CO2 dissous en mol/kg deau. concentrations, determined by an acid and [H2CO3] is thedissolved CO2 concentration titration, referred to as thetotal alkalinity, thus H2CO3 se dissocie en eau selon in mol/kg of water. about equals thecarbonate alkalinity defined as: H CO3 dissociates in water according to H22 CO3 + H+ + HCO3 (9.7) $] = b + 2c (9.15) AC = [HCO!] + 2[CO + H2CO3 + H + HCO! (9.7) If thewater contains Ca2+ (or Mg2+) and carbonet and ate or is in contact with calcite also thedisso+ 2 HCO (9.8) 3 H + + CO3 ciation equilibrium of calcite affects thecarbon HCO ! H + CO$ (9.8) Chimie de lacide carbonique chemistry: ou les conditions dquilibre sont quantifies par les constantes de dissociation ou dacidit: Chimie de lacide carbonique where the equilibrium conditions are quantified + by the dissociation CaCO3 Ca2+ + CO$ (9.16) [H ][HCO 3 ] or acidity constants: 144 K1 = + (9.9) [H ][HCO 3] [H CO ] 2 3 (9.9) K1 = (9.9) are limited by thesoluwhere theconcentrations [H 2 CO 3 ] bility product: and
[H ][CO ] K2 = + [H ][CO ] K 2 = [HCO ] [HCO ]
+ 2 3 2 33 3

[H 2 CO 3 ] PCO2

(9.6)

as humic acids in freshwater or borate, [B(OH) 4 ], in seawater.

(9.6)

KCaCO3 = [Ca2+][CO$] (9.17) (9.10)

(9.10) (9.10) 9.3. Theequilibrium constants

Basically all values of thesolubilities and disChapitre 9dependent. sociation constants are temperature However, theK values (9.11)also depend on thesolute concentrations, because (9.11) theformation of ion com9.3 LES CONSTANTES DEQUILIBRE ions, we will write thehydrated hydrogen ion + plexes between thecarbonic Ici nous devons prciser que, bien que lion hydrogne, H , soit communment hydrat pour former ions and molecules + + as H as thehydrated structure does not K = [H ][OH ] (9.11) + enter and ions in thesolution thedissolved + + w Fondamentalement, toutes les valeurs dehinder solubilit et constantescarde dissociation sont d Ici nous devons prciser bien que lion hydrogne, H , soit communment hydrat pourprise former H3O , nous crirons lionque, hydrogne la structure hydrate nest pas en thechemical models.en tant que H+ puisque bonic molecules and ions to take part in thether+ temprature. Toutefois, valeurs de Ken dpendent aussi des concentrations en solu H lion hydrogne en tant que H puisque la structure hydrate les nest pas prise 3O , nous compte danscrirons les modles chimiques. modynamic equilibrium reactions. Therefore, formation dions complexes entre les ions carboniques et les in ions et molcules compte dans les modles + + chimiques. The[H ] concentration is generally given as apH thethermodynamic equation, theconcentrations de la valeur du pH, dfinie comme son La concentration en [H ] est gnralement donne au travers empche les molcules et les ions de prendre part aux ractions dquilibre thermody value, logarithm: have to be replaced byson their activities, that are ] est as gnralement donne au travers delquation la valeur du pH, dfinie comme La concentration en defined [H+inverse logarithme :thenegative dans thermodynamique, les concentrations doivent tre remplaces par le smaller than theconcentrations. Thethermodylogarithme inverse : 1010 + + sont plus faibles. La constante de (9.12 solubilit log[H ] ] (9.12) ) is:thermodynamique est : pH log[H pH== namic solubility constant
Enfin, la dissociation de leau obit la condition dquilibre suivante Here de weleau have to emphasise that, although Enfin, la dissociation obit la condition dquilibre suivante + + thedissociation thehydrogen ion, H , is commonly hydrated Finally of water obeys theequiKw = [H ][OH ] + condition to form H O+ or even to multiple hydrated librium K w = [H ][OH 3] (9.12) pH = 10log[H+] ou La concentration totale enconcentration carbone inorganique dissous (=inorganic carbone total, galement par CO CO2 ] Thetotal of dissolved a H 2COnote [H 3 a 2 3 = = K ou La concentration totale en carbone inorganique dissous (= carbone total, galement note par CO 0 or carbon (=total carbon, also denoted by S CO 2 C ou DIC) est dfinie comme: 2

grande tels que les acides humiques dans les eaux douces ou les borates, [H CO [B(OH) ] K 4] dans leau deprcision, mer. ' K0 = 2 3 = 0 leau de mer. P 2 a En conditions naturelles, [H+] et [OH] sont ngligeables par comparaison aux CO concentrations des 88 En conditions naturelles, [H+] et [OH ] sont ngligeables comparaison aux concentrations espces carbonates. La somme des concentrations en acides par faibles et en ions alcalins, dtermine des par Les constantes thermodynamique et d acidit apparente (dissociation) des prem espces carbonates. La somme en destant concentrations entotale, acides quivaut faibles etdonc en ions alcalins, dtermine par une titration acide, rfrence qualcalinit presque l alcalinit des dissociations de lacide carbonique (Eqs. 9.6, une titration acide,par: rfrence en tant qualcalinit totale, quivaut donc presque lalcalinit des 9.9 et 9.10) sont maintenant relies par: carbonates dfinie

SC or DIC) is defined by: C ou DIC) est dfinie comme: CT = [CO2aq] + [H2CO3] + [HCO3] + [CO32] = a + b + c (9.13) where in general (9.13) theactivity coefficients < 1 2 C = [CO aq] + [H CO ] + [HCO ] + [CO ] = a + b + c o en gnral, les coefficients dactivit < 1 ( = 1 pour une solution idal T 2 2 3 3 3 = [CO + [H2COdduite !]conservation + [CO$] de llectroneutralit CTune 2aq] pratique, 3] + [HCO Lalcalinit est quantit de la des solutions ou , i.e. with zero solute (=1 for an ideal solution concentration en soluts nulles ou une force ionique nulle). Lalcalinit est une quantit pratique, dduite de conservation de llectroneutralit desor solutions ou strength zero ionic ). les concentrations en ion-mtal (Na, Ca, Mg) et lela pH sont constants : concentrations =a + b + c (9.13) les concentrations en ion-mtal (Na, Ca, Mg) et le pH sont constants Dans les : solution non-idales deaux marines ou de saumures, il est plus pratiqu + 2 The alkalinity is apractical quantity, following In thenon-ideal acides faibles] solutions (9.14) of seawater and brackA T = [HCO3 ] + 2[CO3 ] + [OH ] [H ] + [autres anions ou relations entre les concentrations relles et lesto concentrations mesurables par la consta + 2 of electroneutrality from theconservation in soluish water it is more practical describe therela(9.14) AT = [HCO3 ] + 2[CO3 ] + [OH ] [H ] + [autres anions ou acides faibles] Dans laquelletions les concentrations en dautres acides faibles peuvent tre incluses pour obtenir une plus apparente where themetal-ion concentrations (Na, Ca, : tion between thereal, measurable concentrations plus Dans laquelle les concentrations en dautres acides faibles peuvent tre incluses pour obtenir une grande prcision, tels que les acides humiques dans les eaux douces ou les borates, [B(OH) 4 ] dans Mg) and pH are constant: by the apparent solubility constant:

PCO 2

PCO 2

(9.18a)

Dans solution marines saumures, il est plus pratique les < ou 1 (de = 1 pour une solution idale, de i.e.dcrire avec des o enles gnral, lesnon-idales coefficientsdeaux dactivit apparente : les < 1 ( = 1 pour une solution idale , i.e. avec des o en gnral, les coefficients dactivit relations entre concentrations relles et les concentrations mesurables par la constante de solubilit concentration en soluts nulles ou une force ionique nulle). concentration apparente : en soluts nulles ou une force ionique nulle). Dans les solution non-idales deaux marines ou de saumures, il est plus pratique de dcrire les [H K0 ' 2 CO 3 ] K0 = non-idales = deaux (9.18b)les Dans les solution marines ou de saumures, il est plus dede dcrire relations entre les concentrations et les concentrations mesurables par lapratique constante solubilit relles [HP K CHEMISTRY OF CARBONIC ACID IN WATER CO 2 3 ] a ' 2 CO 0 = relles et les concentrations mesurables par la constante de (9.18b) relations entre solubilit 0 =concentrations apparente : Kles PCO2 a apparente : Les constantes thermodynamique et dacidit apparente (dissociation) des premire et seconde [H 2 CO 3 ] K0 practically equal to those reported by [95] for '' 3 = 0 (Eqs. 9.6, 9.9 et 9.10) sont maintenant relies par: dissociations de0 lacide carbonique K = [H 2 Les constantes thermodynamique et dacidit apparente(9.18b) (dissociation) des premire et(9.18b) seconde K 0 ' freshwater (at S=0): 2 CO 3 ] 0 P = = a (9.18b) CO CO a (Eqs. 2 2 dissociations K de0 lacide carbonique 9.6, 9.9 et 9.10) sont maintenant relies par:

P 2 a + a H aCO H [H ] b [HCO 3 ] HCO3 0.0178471T + 15.5873 pK0 = 2622.38/T = = K (9.19a) The thermodynamic and the apparent acidity 1 Les constantes thermodynamique + dacidit apparente (dissociation) des premire et seconde et a a a [H CO ] [H ] [HCO ] H HCO H CO a 2 3 [96] (9.22) H b of 3 first 2 3 3 (dissociation) constants the and second Les constantes thermodynamique et d acidit apparente (dissociation) des premire et(9.19a) seconde = = K dissociations de carbonique (Eqs. 9.6, 9.9 et 9.10) sont maintenant relies par: 1 lacide a [H CO ] dissociation of carbonic acid (Eqs.9.6, 9.9 and H 2CO a 2 9.6,3 9.9 et 9.10) sont maintenant relies par: 3 dissociations de lacide carbonique (Eqs. pK1 = 3404.71/T + 0.032786T 14.8435 et 9.10) are now related + by: aH a HCO3 H [H + ] b [HCO 3 ] [96] (9.23) H HCO 3 H b 3 = a H a HCO = [H + ] [HCO ] K1 (9.19a) et 1 3 + H [H bCO ] 3 aH = K1' = [H (9.19a) (9.19a) CO a 2 3 ][HCO ] H2 CO a 2 3 3 2 3 3 = K1 = a H K1 a [Ha2 CO pK2 = 2902.39/T + (9.19b) 0.02379T 6.4980 3] +2CO 3 [H [H ][HCO 2 CO 3 ]3 ] H ' ab [97] (9.24) K1 = = K (9.19b) et [H 2 CO 3 ] H b 1 and et lnKw = 148.9802 13847.26/T 23.6521 lnT + [H + ][HCO3 ] a '' a 3 [98] (9.25) + = K1 = K (9.19b) (9.19b) 1 1 [H ][HCO 1 a 3] CO ] = (9.19b) K1' = [H 2 K b 3 H 2 3 H b 1 where theabsolute temperature T=t(oC) + [H 2 CO 3 ] H et, par rapport la deuxime constante de b dissociation: 273.15 K. and with respect to thesecond dissociation conet, par rapport la deuxime constante de dissociation: stant: a a [H + ] [CO 2 ] H CO3 K2 = = H + c 3 (9.20a) 2 9.3.2. Seawater a aCO a b [HCO H [H ] c [CO H HCO 3 ]3 ] 33 K2 la = deuxime =constante de dissociation: (9.20a) (9.20a) et, par rapport a HCO3 constante b [HCO The salt concentration of seawater is defined by 3] et, par rapport la deuxime de dissociation: et the salinity, given in g/kg of seawater, or in . 2 + 2 aH aCO3 H [H + ] c [CO 3 ] and H CO H c 3 3 Probably thebest (9.20a) data have been reported by + 2 K2 et 2 = a H a CO = [H ] [CO 3 ] c 3 + 2 H [HCO a HCO ] K2 = = (9.20a) b 3 [H ][CO ] [95]; these values for thetemperature range of 0 HCO b 3 3 ' 3 3 b = a HCO = (9.20b) K2 K3 b [HCO (9.20b) 2] 2 + 3 to 40C and thesalinity range of 0 to 40 are [HCO ] ] [H ][CO 33 H ' b c = = (9.20b) K2 K et 2 shown in Figs 9.1 to 9.4 and in Table9.1 (right [HCO 3 ]also H c into account that in reet Thedefinition takes 146 hand shaded column). Theseawater values (at + + 2 ality instead of + [H ] thepH is being measured 2 S=35) are practically equal to thevalues pub[H ][CO ] 146 '' b 3 b K 3 + aseries 2 = = [H (9.20b) K2 based on of buffer solutions. Therefore, 2 ][CO ] 2 2 lished by [99, 100], as reported by [101]: ' b 3 [HCO ] = = (9.20b) K K + pH c 3 H c 3 H ]is to2 be replaced by 10 . in 2these[HCO equations [H ] 3 H c 146 Comparing fresh and seawater, thedifferences lnKo = 60.2409 + 9345.17/T 146 in the first and second dissociation constants of + 23.3585 ln(0.01T) + S [0.023517 carbonic acid K1 and K2 for freshwater, and 0.023656 (0.01T) + 0.0047036 (0.01T)2 (9.26) K1 and K2 for seawater and theconsequences thereof will appear spectacular. pK1 = 3670.7/T 62,008 + 9.7944 lnT For practical reasons thevalues of thedissocia0.0118 S + 0.000116 S2 (9.27) tion constants are generally given as:

pK = 10log KorK = 10 pK

(9.21)

The K0, K1 and K2 values for freshwater (ideal solution) and seawater as afunction of thewater temperature and thewater salinity are discussed in thenext section and shown in Figs 9.19.4. 9.3.1. Ideal solutions

pK2 = 1394.7/T + 4.777 0.0184 S + 0.000118 S2 (9.28) (K0: [99]), (K1, K2: [100], reported by [101]. The salinity values S are related to theoriginally used chlorinity, i.e. theconcentration of chloride (+bromide and iodide, also given in g/kg or ), by: S = 1.80655Cl (9.29) Thesolubility product of calcium carbonate differs for thetwo different crystalline types, calcite and aragonite. Figs 9.5 and 9.6 show values at specific temperatures and salinities. 89

Most freshwaters can be considered as ideal solutions (extrapolated to zero ionic strength). Values for thetemperature range of 0 to 40C and thesalinity range of 0 to 40 are shown in Figs.9.1 to 9.4 and in Table9.1 (left-hand shaded column). Theclassic data of Harned and co-authors are

Fig. 9.5. Produit de solubilit (Eq. 9.17) de la calcite (CaCO3) dpendant de la tem salinit de leau pendant la prcipitation (valeurs lEq. 9.43 de (Mucci la tem Fig. 9.5. Produit de solubilit (Eq. 9.17) de la calcite (CaCOselon 3) dpendant
INTRODUCTION

salinit de leau pendant la prcipitation (valeurs selon lEq. 9.43 (Mucci

9.3.3.

As we have mentioned thedifference between thelarge effect of salt concentrations on theacideaux naturelles.des Des exemples seront montrs dans les parties suivantes. La distribution espces de lacide carbonique dissous dans unepour eau pure peut douc tre theacidity constants for thefresh and dacidit seawater ity constants (Fig.9.4), result in an entirely dif- mentionn, Comme les diffrences entre les constantes les eaux une fonction are duCeci carbone inorganique total dissous. A partir des quations 9.6, 9.9tre et 9 considerable. This EN greatly effects thedistribuLa distribution des espces de lacide carbonique dissous dans une eau de pure peut ferent chemical character of freshwater and sea9.4 CONCENTRATIONS ACIDE CARBONIQUE considrables. affecte grandement la distribution des fractions lacide carb tion of thecarbonic acid fractions in natural wa9.20 respectivement, nous obtenons : water, as will be illustrated in thenext sections. une fonction du Des carbone inorganique total dissous. des quations 9.6, 9.9 et 9 eaux naturelles. exemples seront montrs dans A lespartir parties suivantes. Comme mentionn, les diffrences entre les constantes dacidit pour les eaux douc ters. Examples of this Theacidity constants for freshwater with zero 9.20 respectivement, nous obtenons : will be shown in thefolconsidrables. Ceci affecte grandement la distribution fractions lacide carb La distribution des espces de lacide carbonique dissousdes dans une eau de pure peut tre lowing sections. salinity and for seawater have extensively been [H 2 CO 3 ] = K 0 P CO 2 eaux naturelles. Des exemples seront montrs dans les parties suivantes. une fonction du carbone inorganique total dissous. A partir des quations 9.6, 9.9 et 9 studied experimentally. Theproblem remains [H 2 CO 3 ] = K 0 PCO2of thedissolved carbonic acid Thedistribution 9.20 respectivement, nous obtenons : can theproper treatment of waters with varying low species in pure water be specified afrac La distribution des espces de lacide carbonique dissousas dans une -eau pure peut tre salt concentrations. In order to obtain theproper tion of thetotal dissolved inorganic carbon. From une fonction du carbone inorganique total dissous. A partir des quations 9.6, 9.9 et 9 [H 2 CO =K PCO K values, theK values must be corrected with Eqs 9.6, 9.9 and Eqs 9.18, 9.19 3] 0+ 2 [H ] 9.10, 9.20 respectivement, nous obtenons : respectively, [H 2 CO ] = [HCO ] thehelp of theDebye-Hckel theory applicable and 9.20 we obtain: 3 3 K+ [H 1] at low concentrations. Thetreatment of non[H CO ] = [HCO 2 3 3] [H 2 CO 3 ] = K (9.33) 0P CO 2 K ideal solutions is illustrated here by considering 1 freshwaters with less dissolved salts than about [H + ] [H 2 CO 3 ] = [HCO 3 ] (9.34) 400mg/L [102]. K1 K2 2 [CO 3 ] = + +[HCO 3 ] Ameasure for thesalt concentration is theionic [H ] [H K 2 2] [H ]= + [HCO ] strength (I) of thewater. This can be approximat[CO = [HCO (9.35) 2 CO 3 ]3 3 ]3 K [H ] 1 ed by:
ce qui donne
5

considrables. Ceci affecte grandement distribution des fractions carb Comme les diffrences entre la les constantes dacidit pourde leslacide eaux de la douc tem Fig. 9.5. mentionn, Produit deconcentrations solubilit (Eq. 9.17) de la calcite (CaCO 3) dpendant Thelarge differences between K and eaux K , i.e. naturelles. Des exemples seront montrs dans les parties suivantes. considrables. Ceci de affecte la distribution des fractions de 9.43 lacide carb salinit leaugrandement pendant EN la prcipitation (valeurs selon lEq. (Mucci 9.4 CONCENTRATIONS ACIDE CARBONIQUE

Brackish water

9.4 CONCENTRATIONS EN ACIDE CARBONIQUE Fig. 9.5. Produit de solubilit (Eq. 9.17) de la calcite (CaCO3) dpendant de la tem 9.4 CONCENTRATIONS EN ACIDE CARBONIQUE salinit de pendant la prcipitation (valeurs selon lEq. 9.43 (Mucci Comme mentionn, les leau diffrences entre les constantes dacidit pour les eaux douc
9.4. Carbonic acid

0.5 I

+ 1.4 I

K2 so that 2 ce qui donne [CO 3 ]= + [HCO 3 ] I 2.510 S (9.30) + [H ] [H ] K2 +1+ + [HCO 3 ] CT = (9.36) where S is thesalt concentration in mg/L. Theap+K 2 K [H ] K [H ] 2 1 2 [CO ] = [HCO ] ce qui donne CT = 3 3 [HCO 3 ] proximate values for thetwo acidity constants + 1+ K [H+ ] [H + ] Chimie de lacide carbonique 1 then are: Les concentrations fractionnes peuvent tre de maintenant donnes Chimie lacide + Thefractional concentrations can nowcarbonique be given en fonction de la te [H ] K2 ce qui donne 0.5 I 2 I in [HCO ] = + 1 + peuvent CTterms total: of thetotal content: ' concentrations tre donnes en fonction de la te 3 maintenant +carbon fractionnes pK 1' = pK 1 and pK 2 = pKLes K1 [H ]+ 2 K [H ] 1 total: 1 + 1.4 I I CT ] =+ + 2 [H + 152 1 + 1.4 [HCO + ]K 1+K 3 [H ] ] +K [H [H 1K 2 C 2 ]K1 [HCO ] = (9.37) [HCO 3 1]+ ]K T ++ CT = 2 3 maintenant 152 + + fractionnes Les concentrations donnes en fonction de la te [H +peuvent [H ]K1 tre +K 2 I ' 1 2 K [H ] 1 and pK 2 = pK 2 (9.31) total: 1 + 1.4 I [H + ]2 CT en fonction de la te [H CO ] = [CO aq] = + 2 Les concentrations fractionnes peuvent tre maintenant donnes 152 [95] + ] 2 3 2 [H Theacidity constant values published by [H + ]2 + [H ]K1 + K1 K 2 C [H CO ] = [CO aq] = T 2 3 2 total: [H + ]2 + [H + ]K1 + K1 K 2 are derived from theabove considerations on (9.38) non-ideal solutions taking into account aseries 152 K K2 2 of different compounds. Sets of data for various (9.39) CT [CO 3 ] = + 2 K1 +K 2 2 +K K ]K temperatures and salinities are further presented 1 1 2 C [CO 3 ] = [H + ]2 + [H 1 T + [H ] + [H ]K1 + K1 K 2 in Table9.1. and likewise for theapparent acidity constants K peu prs de faon identique pour les constantes dacidit apparentes K' dans de Values of thesolubility product of etcalcite in non-ideal solutions such as seawater. et peu prs que de faon identique idales telles leau de mer. pour les constantes dacidit apparentes K' dans de (CaCO3) (Eq.9.17) used in this volume are taken Therelative contributions of [H2CO3], [HCO!] idales telles que leau de mer. 2 from [103]: ], [HCOcontent ] dans la teneur en ca Les contributions relatives [H2CO3carbon and [CO$ ] to de thetotal is 32 shown 3 ] et [CO CO ], [HCO ] et [CO dans diffrentes, la teneur en ca Les contributions relatives de [H 2 du 3 pH of 3 deux 3 ] difindiques sur la Fig. Fig. 9.6 fonction pour tempratures pour in 9.6 en as afunction pH for two pKcal = 10logKcal = 171.9065 + 0.077993T indiques sur la Fig. 9.6 en du pH pour deux tempratures diffrentes, ferent temperatures for freshwater (at (S ionic (de force ionique nulle) et enfonction moyenne pour les eaux marines = 35,0 ou Cl =pour 19,3 strength=0) average (S=35.0 nulle) et enand moyenne pourseawater les eaux marines (S = 35,0 ou Cl = 19,3 2839.319/T 71.595 logT + (0.77712 (de force ionique Comme nous lavons anticip, les constantes dacidit de lacide carbonique change or Cl=19.37). 0.0028426 T 178.34 / T)S1/2 + 0.07711 S
3/2

Values are shown in Fig. 9.5 as functions of thewater temperature for fresh- and seawater 9.5 and as afunction of salinity at 20C. 9.5 90

Comme nous lavons les constantes dacidit decela lacide carbonique avec la temprature et anticip, la force ionique de la solution que produit une trs change forte d As was anticipated, theacidity constants of car 0.0041249 S (9.32) avec la temprature la ionique et dela la solution que cela produit une trs forte d distribution la fois et sur laforce temprature salinit. bonic acid change so rapidly with temperature distribution la fois sur la temprature et la salinit.

Dans ce paragraphe, quelques exemples seront donns sur la manire de rsoud Dans ce paragraphe, quelques exemples seront surclos la manire de rsoud mentionnes ci-dessus. Nous nous rfrerons auxdonns systmes dans lesquels les mentionnes ci-dessus. Nous nous rfrerons aux systmes clos dans lesquels les ou carbonique nchangent pas, que ce soit avec le systme gaz (CO2 atmosphrique ou carbonique nchangent pas, que ce avec leouvert, systme (CO2 atmosphrique la phase solide (CaCO3 ). Dans unsoit systme lagaz solution change soit ave la phase solide (CaCO ). Dans un systme ouvert, la solution change soit ave (= systme ouvert sur la 3phase gaz), ou avec le solide (ouvert sur CaCO3). Nous allon Nous allon (= systme sur la phase gaz), avec le (ouvert CaCO 3). en avec (i) laouvert comparaison entre eauou douce etsolide eau de mer,sur les deux quilib

and with theionic strength of thesolution that it results in astrong dependenceOUVERTS of thedistribution EXEMPLES SUR SYSTEMES ET FERMES on both temperature and salinity. EXEMPLES SUR SYSTEMES OUVERTS ET FERMES

CHEMISTRY OF CARBONIC ACID IN WATER

TABLE 8.1. Apparent solubility and acidity (dissociation) constants of carbonic acid for various temperatures and salinities. Thevalues are according to [95].
K0 102 t (C) 0 5 10 15 20 25 30 35 40 K1 107 t (C) 0 5 10 15 20 25 30 35 40 0 2.667 3.069 3.467 3.846 4.188 4.498 4.753 4.966 5.105 5 4.667 5.420 6.194 6.966 7.727 8.433 9.099 9.705 10.26 10 5.433 6.353 7.295 8.241 9.183 10.09 10.96 11.80 12.56 15 5.984 7.015 8.072 9.162 10.26 11.32 12.36 13.37 14.32 20 6.412 7.534 8.690 9.908 11.12 12.33 13.52 14.69 15.81 25 6.761 7.962 9.204 10.52 11.83 13.18 14.49 15.81 17.06 30 7.047 8.299 9.638 11.04 12.45 13.90 15.35 16.79 18.20 35 7.278 8.610 10.00 11.48 13.00 14.52 16.11 17.66 19.19 40 7.464 8.851 10.30 11.86 13.46 15.07 16.75 18.41 20.09 0 7.691 6.383 5.370 4.571 3.936 3.428 3.013 2.679 2.404 5 7.499 6.223 5.236 4.457 3.837 3.342 2.938 2.612 2.344 10 7.295 6.067 5.105 4.345 3.741 3.258 2.864 2.547 2.286 15 7.112 5.916 4.977 4.236 3.648 3.177 2.793 2.483 2.223 S () 20 6.934 5.754 4.842 4.121 3.556 3.090 2.723 2.415 2.168 25 6.761 5.610 4.721 4.018 3.459 3.013 2.655 2.355 2.113 30 6.592 5.470 4.603 3.917 3.373 2.938 2.582 2.296 2.061 35 6.412 5.321 4.477 3.811 3.289 2.858 2.518 2.234 2.004 40 6.252 5.188 4.365 3.715 3.199 2.786 2.449 2.178 1.954

K2 1010 t (C) 0 5 10 15 20 25 30 35 40 0 0.240 0.284 0.331 0.380 0.430 0.479 0.527 0.573 0.617 5 1.291 1.600 1.950 2.350 2.793 3.289 3.828 4.426 5.070 10 1.879 2.339 2.877 3.491 4.188 4.966 5.834 6.792 7.870 15 2.355 2.951 3.639 4.436 5.346 6.383 7.534 8.831 10.28 20 2.773 3.491 4.325 5.284 6.397 7.656 9.099 10.72 12.53 25 3.155 3.981 4.943 6.081 7.379 8.872 10.57 12.50 14.69 30 3.508 4.436 5.534 6.823 8.299 10.02 11.99 14.22 16.79 35 3.837 4.864 6.095 7.516 9.183 11.12 13.34 15.89 18.79 40 4.150 5.272 6.607 8.185 10.05 12.19 14.66 17.50 20.75

91

Freshwater S = 0 6

K 0' 10 2

5
5

INTRODUCTION
3 2 8 7 Freshwater S = 0 6 0 5 10 15 20 25 30 Seawater S = 35
25

15

35

40

t ( oC)
4 3.8
5

[96] Harned & Davis, 1943

K 0' 10 2

K 0' 10 2

5 4 3 2 0 5 10 15 20 25 30 35 40 Seawater S = 35

3.6 25 3.4 20 3.2 3 15 10 Seawater S = 35

[95] Millero & Roy, 1997

15

25

t = 20 oC 0 5 10 15

K 1' 10 7

25

20

25

30

35

t ( C)

S ( or g/kg)
5

15

40

K 0' 10 2

4 9.1. Thesolubility constants (=solubilities in M/L.atm) for CO in freshwater, seawater and brackish water Fig. 2 [96] Harned & Davis, 1943 5 as afunction of temperature at salinities of 0, 5, 15, 25, and 35 (=g of salt per kg of water) (upper graph) and 3.8 S=0 as afunction of salinity at 20C (lower graph). All values are according to [95], at higher salinities similar to 0 3.6 [99] (Eq.9.26); thevalues for freshwater are &similar [95] Millero Roy, 1997 to those of 0 [96] 5 (Eq.9.22). 10 15 20 25 30 35 40 3.4 25 3.2 3 20 0

t ( oC)
t = 20 oC 5 10 15 Seawater 20 S = 35 25 30 35
25 15

6 40 Freshwater S = 0 5

K 1' 10 7

K 1 107

15 10

S ( or g/kg)

5 S=0 0 0 5 10 15 20 25 30 35 40

3
25

2
20 0

10

15

20
o

25

30

35

40

t ( oC)
K 2' 10 10
15

t ( C) S = 35 Seawater
25

K 1 107

Fig. 9.2. The acidity constants for the first dissociation of carbonic acid in freshwater and seawater as a function 15 10 Freshwater S = 0 of the water temperature at salinities of 0, 5, 15, 25, and 35. The values are according to [95]. The freshwater 5 values are equal to those of [96] (Eq. 9.23), the marine values are in good agreement with those reported 5 by 5 [100] as discussed by [101] (Eq. 9.27).
4
S=0
35 0

3 25 2 20 0
10

10

15

20

25

30

40

t ( oC)
0.8

10

15

20 Seawater S 25 = 35 30

35
25 15

40
0.6

K 2' 10

15

t ( oC)

Freshwater S = 0

10

S=0
0 0 5 10 15 20 25 30 35 40

K 2 1010

0.4

0.2 0 5 10 15 20 25 30 35 40

t ( oC)
0.8

t ( oC)

92

K 2 10

Fig. 9.3. Theacidity constants for thesecond dissociation of carbonic acid in freshwater and seawater as afunction of thewater temperature at salinities of 0, 5, 15, 25, and 35. Thevalues are according to [95]. ThefreshFreshwater S = 0 water 0.6 values are equal to those of [97] (Eq.9.24), themarine values are in good agreement with those reported by [100] as reported by [101] (Eq.9.28).
10

0.4

0.2 0 5 10 15 20 25 30 35 40

t ( oC)

12

[95] Millero & Roy, 1997

K 1' 10 7

10 8 6 4 0 5

CHEMISTRY OF CARBONIC ACID IN WATER

[96] Harned & Davies, 1943

10 15

S ()

20

25

30

35

40

14

K 1' at t = 20 oC
12

12 10

K 2' at t = 20 oC

[95] Millero & Roy, 1997

K 1' 10 7

K 2' 10 10

10 8 6 4 0 5

8 6

[95] Millero & Roy, 1997

4 2

[96] Harned & Davies, 1943

10 15

0
20 25 30 35 40

[97] Harned & Scholes, 1941

0 5 10 15 20 25 30 35 40

S ()

S ()

12

Fig. 9.4. Values for thefirst and second dissociation constants of dissolved carbonic acid as afunction of thesa10 linity [95]. Thevalues are valid for awater temperature of 20C.
8 6

K 2' at t = 20 oC

K 2' 10 10

[95] Millero & Roy, 1997

4 2

4.4 4.2

0 0 5

[97] Harned & Scholes, 1941

10 15 20

Seawater S = 35
25 30

35

40

9.5. Examples for open and closed systems In this section afew examples will be given of how to deal with theabove equations. We will refer to closed systems in which thedissolved carbonic acid fractions do not exchange, nor with thegaseous system (atmospheric or soil CO2), neither thesolid phase (CaCO3). In an open system thesolution exchanges with either thegaseous phase (=open to thegas phase), or thesolid (open to CaCO3). We will be dealing with (i) acomparison with fresh and seawater, both in equilibrium with atmospheric CO2, (ii) agroundwater sample of which [H2CO3] corresponds to a PCO2 value far exceeding theatmospheric concentration and which is brought into contact with theatmosphere at aconstant temperature, (iii) water exposed to theatmosphere in thepresence of calcium carbonate rock, and (iv) mixing freshwater and seawater (in an estuary) under closed conditions. 9.5.1. Comparison of freshwater and seawater exposed to theatmosphere

S ()

K cal ' 10 7
4 0
4.5 4 3.5 3 2.5

t ( oC)
10 15 20 25 30 35 40

Freshwater S = 0

K cal 109
2 0
6 5 4 3 2 1

t ( oC)
10 15 20 25 30 35 40

K cal ' 10 7

t = 20 oC

S ()
0
0 5 10 15 20 25 30 35 40

Fig. 9.5. The solubility product (Eq.9.17) of calcite (CaCO3) depending on the water temperature and salinity during precipitation (values according to Eq.9.43 [103]).

Here we are dealing with an open system to theatmosphere (exchange with atmospheric CO2) at aconstant temperature. Thelatter is considered to be of infinite dimensions, so that PCO2 is constant. Thesystem is closed to CaCO3, so that thecarbonate alkalinity (=theconcentration of 93

INTRODUCTION

positive metal ions) is constant. Thegiven conditions are shown in Fig.9.7. Here we will use thesymbols: a = [H2CO3] + [CO2aq] b = [HCO!]c = [CO$] Thevalues of thefirst and second (apparent) acidity constants are calculated from Eqs 9.22 to 9.28. Furthermore, we apply theEqs 9.37 to 9.39 for calculating thevarious dissolved fractions. Starting with theknown value of theatmospheric partial pressure of CO2, thedissolved CO2 concentration is obtained, and from that thepH dependent other concentrations. 9.5.1.1. For freshwater a = [H2CO3] = K0PCO2 = 0.04571(M/L.atm) 350106(atm) = 1.600105 M/L b = [HCO!] = (K1/[H+])a = (3.846107/[H+])a = 6.1541012/[H+] c = [CO32] = (K1K2/[H+]2)a = (3.8461073.800 1011/[H+]2)a = 2.3381022/[H+]2 Thecarbonate alkalinity is known:
2 [H 2CO 3], [HCO3 ], [CO 3 ] / C T (%)

AC = b + 2c = 6.1541012/[H+] + 4.677 1022/[H+]2 = 2.2103 M/L From this quadratic equation [H+] and thepH can be obtained, resulting in: [H+] = 2.871 109 M/L and pH = 8.542 Thetotal carbon content of thewater then is obtained by inserting [H+] in theabove equations: CT = a + b + c = 0.016 + 2.14 + 0.028 = 2,19 mM/L 9.5.1.2. For seawater a = 0.03811(M/kg.atm) 350106(atm) = 1.334105 M/kg b = (11.480107/[H+])1.334105 = 15.3141012/[H+] c = (11.4801077.5161010/[H+]2) 1.334 105 = 1.1511020/[H+]2 Again thecarbonate alkalinity is known:

100 100

H 2CO 3
80 80

HCO 3

HCO

2 CO 3

60 60

S=
40 40

35

0 5 0C 25 0C

35

20 20

HCO 3 H 2CO
4 4

CO 2 3

HCO 3

0 0 55 6
6

pH

9 10

10 11

11

12 12

Fig. 9.6. Distribution of thecarbonic acid fractions as percentages of thetotal carbon content, CT. Thevalues are calculated using Eqs 9.37, 9.38, 9.39 for temperatures of 5 and 10C and for salinities of 0 and 35 as afunction of thepH. Seawater has pH values around 8.2. However, thecarbon distributions are shown for an (unrealistic) wider range of pH values, to illustrate thedependence of thecarbon distribution on salinity.

94

CHEMISTRY OF CARBONIC ACID IN WATER

Fig. 9.7. Schematic representation of theconditions of fresh (0) and seawater (35), both in equilibrium at aconstant temperature with theatmosphere with constant CO2 concentration (partial pressure). Theupper part shows thegiven conditions, thelower part theresulting data.

b + 2c = 15.311012/[H+] + 2.3021020/[H+]2 = 2.2103 M/kg Solving this quadratic equation results in: [H+] = 8.232109 M/kg et pH = 8,084 Thetotal carbon content is: CT = 0.013 + 1.86 + 0.170 = 2.04 mM/kg

ions and apossible precipitation of calcite (open to thesolid phase). 9.5.2.1. Starting conditions We assume that thetemperature, pH (resulting in [H+]=10-pH) and thetitration alkalinity (A) are Chimie de lacide carbonique known by measurement. TheH+ concentration will be denoted by thesymbol h instead of [H+].

Nous pouvons utiliser les quations: Comparison of these results, as shown in Fig.9.7, We can use theequations: reveals that in thefreshwater thecarbonic species A = b + 2c + 1014.34 /h/h h, h, owhere les deux derniers2 termes A= b + 2c + 1014,34 thelatter termspeuvent tre nglig consists for 98% of dissolved bicarbonate, while can=be /h K1neglected theseawater with alower pH still contains about b/a 10% of dissolved carbonate ions. b/a =K K 1/h c/b = 2/h

9.5.2.

c/a= K1K2/h2 or c=(K1K2/h2) a avec Thesecond example describes thechemical With changes in acertain given fresh (ground)water A = b + 2c from which excess CO2 escapes to theatmoA= b + 2c ce qui donne: saturasphere and in which CaCO3 precipitates at this results in: tion. In part (1) we shall indicate how thevarious A = (K1 / h) a + (2K1K2 / h2) a carbon concentrations are calculated. In part (2) A= (K1 / h) a+ (2K1K2 / h2)a ainsi: thesolution looses CO2 to theair (open to theatso that: mosphere) at constant temperature until chemical h2 equilibrium between PCO2 and thedissolved CO2 a= A hK1 + 2 K1 K 2 fraction. Part (3) considers thepresence of Ca2+
b= hK1 h A= A hK1 + 2 K1 K 2 h + 2K 2 K1 K 2 K2

System open for CO2 escape and CaCO3 formation

c/b= 2/hdeux dernires relations donne: La multiplication deK ces

2 Multiplication = (K1K2/htwo ) a relations gives: c/a = K1K2/h2 orofcthelatter

(9.40)

95

ainsi: ainsi:

h2 a= A h2 a = hK1 + 2 K1 K 2 A hK1 + 2 K1 K 2

INTRODUCTION

(9.40) (9.40)

hK1 h b= A= A hK1 h b = hK1 + 2 K1 K 2 A = h + 2 K 2 A hK1 + 2 K1 K 2 h + 2K 2

(9.41)

(9.41)of CaCO3 9.5.2.3. Precipitation

K1 K 2 K c= A = K2 A (9.42) K1 K 2 2K c = hK1 + 2 K1 K 2 A = h + 2 2 A hK1 + 2 K1 K 2 h + 2K 2 i.e. 3 equations with 3 unknowns. At atemperai.e. 3 quations avec 3 inconnues. A une temprature de 15C, une valeur de pH de dmarrage de 6.0 2+ Theamount of calcite ture of 3 15 C, astarting value ofde 6.0 and an valeur i.e. 3 quations inconnues. A unepH temprature 15 C, une pH de dmarrage de (or 6.0 Ca ) removed from et une alcalinit avec de 2 mM/L, les concentrations finales sont donnes en Fig. de 9.8 phase 1. 2+ thewater, D1. [Ca ], equals theamount of carbon alkalinity of 2mM/L theresulting concentrations et une alcalinit de 2 mM/L, les concentrations finales sont donnes en Fig. 9.8 phase removed from thewater, DCT. We then have are given in Fig.9.8 phase 1. 9.5.2.2 LIBERATION DE CO2 thefollowing equations: 9.5.2.2 LIBERATION DE CO2 Si leau perd du CO2 lors du contact avec latmosphre, et, en premier abord, si lon nglige la 9.5.2.2. Escape of CO a2= K0p= a1lon =anglige la Si leau perd du abord, si 2+ CO lors du contact 2avec latmosphre, et, en premier
a = K0p thepresence of Ca2+, until equilibrium with theata = K0p 2 A2 A1=[Ca2+]2 [Ca2+]1=CT2 CT1 mospheric PCO2 (denoted by p) has been reached, /(ac) = K1/K b 2 2 /(ac ) = K1/K2 b or [Ca2+]=CT we have: A b + 2c A b 2c a= K+ pKcal 2+ 0p [Ca2+]2 c2=10 or ([Ca De nouveau 3 quations avec 3 inconnues (en gras). Avec les valeurs additionnelles de dpart pour la ]1 + CT)c2=Kcal 2quations avec 3 inconnues (en gras). Avec les valeurs additionnelles de dpart pour la De nouveau /(ac)=K1/K2 (p), la concentration peut tre calcule (Fig. 9.8, phase 2). b teneur en CO3 2 atmosphrique 9.8, phase teneur en CO2 atmosphrique (p), la concentration peut tre calcule (Fig. C =( a+ 2). b + c ) (a+ b + c ) prsence de prsence de nous avons: nous avons:

Here we have, apart from theknown atmospheric PCO2, theadditional complication that calcite 2+ 2precipitates if theproduct (9.42) of [Ca ] and [CO3 ] (9.42) exceeds thesolubility product given by Eq.9.32 (Fig.9.5), so that CA decreases.

(9.41)

mosphere, and in the first instance neglecting

2 ce que lquilibre avec la PCO2 atmosphrique (note par p) soit atteinte, Ca , jusqu 2+ , jusqu que lquilibre avec la with PCO2 atmosphrique (note par p) soit atteinte, Ca theatIf thewater ce looses CO2 in contact

b2/c2 =b1/c1 =(K1/K2)aor c2=(c1/b1)b2

A b + 2c

again 3 equations with 3 unknowns (bald type). With theadditional starting values for theatmospheric CO2 concentration (p), theconcentration can be calculated (Fig.9.8, phase 2).

or CT=b2 + c2 (b1 + c1) For reasons of simplicity we assume that thealkalinity is balanced by theCa2+ ions alone, so that
157 [Ca2+]1=0.5A 157

Fig. 9.8. Schematic representation of thenumerical results from exposing awater sample with given conditions (upper part of 1) to the atmosphere (upper part of 2) and allowing precipitation of calcite (upper part of 3). Thelower part of theboxes show thecalculated data. All concentrations are in M/kg.

96

Chapitre 9

9.5.4

SYSTEME FERME, MELANGE ENTRE EAU DOUCE ET EAU DE

13

CHEMISTRY OF CARBONIC ACID IN WATER

Pour illustrer un systme clos, nous allons discuter du mlange entre une eau douce eau de mer, tel que cela se produit dans les estuaires. Le calcul de
13

de, par exem

Thesolution of this equation theresulting where thesubscript (1) refers to thevalues ob des bicarbonates des deux ples d bicarbonate du mlange partir des valeurs de and Avalues for 4 different temperatures are shown tained by step 2, and (2) to the final values af- parce pas direct que le processus de mlange des fractions molaires de bicarbo in Fig.9.10. Also thecorresponding pH values ter precipitation of CaCO3. These 4 independent conservatif, cest--dire que les quilibres de dissociation de lacide carbonique vol are indicated. equations with 4 unknowns (bald type) can now des changements de pH, et les valeurs des constantes dacidit changent en fonction d be solved. Thenumerical result is shown in la salinit de leau. Fig.9.8. 9.5.4. Closed system, mixing of Comparison of boxes 1 and 2 shows that: freshwater and seawater (1) theamount of CO2 escaped to theatmosphere (=143mL STP) is of theorder of theamount of dissolved CO2 present at thestart of theexperiment;

As an example of aclosed system we will discuss themixing of fresh river water and seawater, such as occurs in an estuary. Calculating 13 of, for instance, thebicarbonate fraction of thebrackish mixture from the13 values of bicarbonate (2) theamount of calcite formed is 25.4mg/L in theend members (fresh and seawater) is not straightforward, because themixing process of themole fractions of bicarbonate is not conser9.5.3. System exposed to CO2 in vative, i.e. thedissociation equilibria of carbonic thepresence of Caco3 Fig. 9.10. Reprsentation schmatique dun systme ouvert, consistant en une masse deau en change acid shift by thechanges pH, and thevalues of In avec thepresence of carbonate rock water may be Les alcalinits sont calcules un rservoir de CO2 infini et une roche carbonate. theacidity constants change by thechanges in exposed to acertain CO2 pressure. Thequestion thesalinity of indiques thewater. Thesystem of thetwo pour 4 tempratures diffrentes. Les valeurs de pH correspondantes sont dans le un systme ouvert, consistant en une masse deau en change Fig. 9.10. Reprsentation schmatique dun ouvert, consistant en une masse deau en change is how much CaCO3 can besystme dissolved in Fig. equilib9.11. Reprsentation schmatique de la formation dune components together is closed, however, so saumure that, par mlange d graphique, ainsi que la pression partielle de CO2 (PCO2). Les alcalinits sont calcules nfini et une roche avec carbonate. Les alcalinits sont calcules un rservoir de CO rium with theCO 2 infini et une roche carbonate.(rivire) 2 atmosphere. et dune eau de mer. Dans le systme ferm choisi, les paramtr if theend members are denoted by f(resh) and tes. Les valeurs depour pH correspondantes sont indiques le de pH correspondantes sont indiques dans le 4 tempratures diffrentes. Lesdans valeurs la figure sont supposs conservatifs. m(arine), the final values for the conservative pressure, Instead of choosing theCO un systme de ouvert, consistant en une masse deau changethecalcu2 en on partielle CO 2 (PCO2). graphique, ainsi que latheeasiest pression partielle de CO2 (P CO2). parameters, i.e. thesalinity, lation procedure is if we depart from procdure de calcul est simplifie si lon commence depuis le thealkalinity and lieu de dfinir la pression de CO2, lasont infini et Au une roche carbonate. Les alcalinits calcules thetotal carbon content, are: thefinal pHatteindre. thewater will obtain. Thealkalinity final de que leau doit Lalcalinit tant dfinie par le principe dlectroneutralit: ntes. LespH valeurs pH correspondantes sont indiques dans le Le systme form de ces deux composants est toutefois clos, ce qui implique que, s isest defined requirement: ). by theelectroneutrality sion partielle de procdure de calcul simplifie side lon commence depuis le 2 (P CO2 est simplifie si lon commence le Au lieu de CO dfinir la pression CO 2, la procdure de calcul nS = n S + n Smm(eau ou depuis S=(n (nm/n)S f f m f/n)S f +valeurs m sont nots par f(eau douce) et de mer), les finales pour les paramtres c K 2 K cal 2+ + 2 w nit tant dfinie par le principe dlectroneutralit: (9.44) pH final que leau tant 3dfinie par le principe dlectroneutralit: h b c A = 2doit Ca atteindre. + [H ] =Lalcalinit [HCO 3 + 2[CO ] + [OH ] = + = + 2 + (9.45) salinit, lalcalinit et la teneur c h total en carbone, sont: where procdure de calcul est si lon commence depuis le 2 K simplifie K 2 cal K 2 K cal nS = nfSf + n 2+ + h = w 2 wm ou S = (nf/n)Sf + (nm/n)Sm (9.44) 2[CO 3 ] ] =2 b9.34 + [OHA +[HCO 2cet + 9.35 mS (9.44) bm c+ Ca + 9.33, [H + dlectroneutralit: ] = + 2[CO ] + [OH ] = +hn =+ +2 Linsertion des donnelquation: 3 3 init tant dfinie = par lecEqs. principe et Sm 35 (Fig.9.11). = n , Sf 0(9.44) h c h

avec n + m = Measurement n, S 0 et Smof 35 (Fig. 9.11). thesalinity of thebrackish waInserting 9.34 and K w 9.35 K cal h 2 f K1 theEqs.9.33, K0 K K2 K0cal K 2K results in nnelquation: 2 19.35 w2 Linsertion des Eqs. 9.33, 9.34 et donnelquation: + 2 P + h P + 2 = 0 (9.44) h b c + 2[CO 3 ] + [OH ] = + = + 2 + ter results in the(degree of) brackishness of CO CO 2 theequation: de la salinit de la saumure correspond la (degr(X) de) saumurisation (X) h2 h 2 h K0K ch La mesure 1K 2

thewater, here defined as thefraction of seawater 2 ici comme la fraction deau de mer (pour leau de mer, X =1, pour leau douce, X 0): K h2 K K K 2 Kw cal K K K K h (for seawater X=1, for freshwater X 0): + h PCO2 + 2 0 1 + 2 =0 0 1 2 P + w h P + 2 cal =0 onnelquation: CO 2 CO 2 de cette de A rsultantes pour 4 tempratures sont illustres sur la h Lasolution 2 h0 K1 Kquation h 2 etles valeurs K K K nf K h 0 1 2 n n n Fig. 9.10. Les valeurs de pH correspondantes sont galement indiques. S= S f + m S m = 1 m S f + m S m 2 n n n n K caltempratures h KA w rsultantes rs illustres sur la h PCO2de +pour 2 4 = 0et lessont + de solution cette quation valeurs de A rsultantes pour 4 tempratures sont illustres sur la La h K 0 K1 K 2 sont Les valeurs ntes indiques. ouindiques. or Fig.galement 9.10. de pH correspondantes sont galement 159
X = S Sf nm S 159 = n S m S f 35

urs de A rsultantes pour 4 tempratures sont illustres sur la 159 antes sont galement indiques. 159 160

Fig. 9.9. Schematic representation of an open system, consisting of awater mass in open contact with aCO2 atmosphere and with solid CaCO3.

97

INTRODUCTION

Theconsequence of this non-linear behaviour of thepH, and thus also of thecarbonic acid fracatmospheric CO tions, is that also 13 of these fractions does not 16 Fig. 9.11. Reprsentation schmatique de la formation dune saumure par mlange dune eau douce 10 obey conservative mixing (Sect.7.3).
20
0
2

avec n + m = n, Sf 0 et Sm 35 (Fig. 9.11). Fig. 9.10. Schematic representation of an open sys13 13 CT 13RDIC a Rb + c 13Rc a + bdfinie La mesure de la salinit de la saumure correspond la (degr de) saumurisation = (X) de R leau, tem, consisting of a water mass in exchange with 13 = a13 Rb + b 13Rb + c 13c/b13Rb (9.49) infinite COde with carbonate rock. ici comme laan fraction deau mer (pourand leau de mer, X =1, pour leau douce, X 0): a/b 2 reservoir Thealkalinities are calculated for 4 different temperaor with R/Rstd=1 + : n n values n indicated in pH tures.n The corresponding are f S f + m S m = 1 m S f + m S m S= thegraph CO n as well n as theatmospheric n n 2 partial pres CT 13DIC=a13a + b 13b + c 13c = a(13b 13a/b) sure (PCO2). + b 13b + c(13c 13c/b) = CT 13b a13a/b c 13c/b ou

values of thedissolved carbonic components in water is by quantitatively converting theDIC 7 8 6 into dissolved CO2 by theaddition of acid (such Le systme form de ces deux composants est toutefois clos, ce qui implique que, si les deux ples as H3PO4) to thewater sample and extracting sont nots par f(eau douce) et m(eau paramtres conservs, i.e. la 13 8 de mer), les valeurs finales pour les 4 theCO 2 from thewater. Consequently only DIC pH = 9 13 salinit, lalcalinit et la teneur total en carbone, sont: can be obtained. If of theconstituting fractions (a, b and c) are to be known, these should 0 ou 3 S = (nf/n) Sf + (nm/1 n)Sm (9.45) nS = nfS 5f + nmSm 4 2 0 be calculated from the13C mass balance (cf. 10 10 10 10 10 10 P CO2 Sect.4.3.1):
A (mM/L)
13

(rivire) et dune eau de mer. Dans le systme ferm choisi, les paramtres prsents sur 20 Theonly possible procedure for determining 12 la figure sont supposs conservatifs.
t ( C)
30
o

S Sf n S X = m = n S m S f 35

9.50) so that
13

(9.46)

(9.46)

Furthermore:
160

DIC=13b (a/CT)13a/b (c/CT)13c/b

(9.51)

nA=nfAf + nmAm or A= (1 X)Af + Am

and similarly: (9.47)

13

DIC=13a (b/CT)13b/a (c/CT)13c/a (9.52) DIC=13c (a/CT)13a/c (b/CT)13b/c (9.53)

and

13

CT=nfCTf + nmCTm or CT=(1 X)Cf + Cm where the13 values are given in Table7.2.

(9.48)

In order to calculate 13a and 13b and 13c thecarbonic acid fractions have to be obtained by solving thefollowing 4 equations with 4 unknowns (in bald type): A= b + 2c CT=a+ b + c K1=hb/a K2=hc/b where again h=[H+], a= [CO2], b=[HCO!] and c=[CO$]. K1 and K2 refer to thebrackish water values at theproper salinity. Astriking feature of estuaries is thenon-linear behaviour of pH as afunction of salinity. Examples were shown by [104]. Theposition of thepH minimum strongly depends on thecarbonate alkalinity ratio of thefresh and marine components (CAf/CAm). 98

FRESH nf A f S fC Tf

SEA nm A m S mCTm

BRACKISH n S A CT

Fig. 9.11. Schematic representation of the formation of brackish water as amixture of fresh (river) and seawater. In thesupposedly closed system theparameters shown in thefigure are conservative.

10. Water sampling and laboratory treatment

This chapter on field and specifically on laboratory practice serves to give thehydrologist as well as thebeginning laboratory worker an impression of theexperimental efforts involved in applying isotope hydrology. Afew parts have been taken -and slightly adjusted- from theIAEA Guidelines / Manual for Operation of an Isotope Hydrology Laboratory. Detailed descriptions of the field practice have been given by Clark and Fritz (see Recommended Literature). We have intended to limit theamount of detail on theanalytical methods, so that thecontents of (parts of) this chapter are valid for any isotope laboratory. 10.1. Water sampling and storage In asuccessful field sampling programme avolume of water is to be collected and brought or sent to theisotope laboratory that is representative for thewater mass under investigation. Themain concern during sampling, transport and storage is to avoid isotope fractionation through evaporation or diffusive loss of water vapour, and/or isotope exchange with thesurroundings as well as with thebottle material. These effects can be minimised by using appropriate collection methods and bottles. Acareful selection and testing of themethods and bottles needs to be made at an early stage. This section provides thebackground information to help in this selection. Thehydrologist, however, should follow thespecific instructions to be given by thelaboratory that is intended to analyse thesamples. 10.1.1. Sampling bottles Thebottle and seal must be made of such adesign and appropriate material that any loss by evaporation and diffusion to or exchange of water with thesurroundings is prevented. Theisotope effect of evaporation can be significant: a 10% loss of sample results in an isotope enrichment of about 10 in 2H and 2 in 18O. Thefollowing conclusions are gained by experience: themost secure vessels for storage are glass bottles, allowing storage of at least adecade as long as theseal is not broken; high-density polyethylene is satisfactory for collection and storage during afew months (water and carbon dioxide easily diffuse through low-density plastics); bottles with small necks are themost satisfactory; caps with positive seals (plastic inserts, neoprene, etc.) are required; thevolume of bottles should normally be 50mL for thecombination of 2H and 18O analyses, 50L for conventional 14C dating and 250mL for AMS 14C dating (Chapter11), and 500mL for low-level 3H analysis. If thestorage may be longer than several months, it is preferable to collect alarger volume and store thesamples in glass bottles (therelative influence of evaporation is than minimised). Generally, thedissolved carbon content of large-volume 14C samples are treated in thefield (see below). Further details on sample quantities are also given in VolumeIV. 10.1.2. General field practice The following points emphasise good field practice that is applicable to all types of water to be sampled (precipitation, surface water, groundwater): always use a field note book to record observations and record numbers data on sample collection sheets to be handed over to thelaboratory determine geographical co-ordinates of sampling points using GPS or national co-ordinate systems, maps, aerial photographs, etc.; measure altitude, depth to thewater table (groundwater), sample depth (depth into groundwater or surface water), well condition, condition of rain gauge, discharge (rivers, artesian wells), lake level, weather conditions, etc.; it is very important to record other chemical and physical data to aid interpretation such as water temperature, pH, alkalinity, conductivity, and other possible chemical constituents

INTRODUCTION

fill sample bottles completely, provided thewater has no chance of freezing during air transport (in that case fill thebottles twothirds full) mark all bottles individually with waterproof marker (project code, location, date, sample number, collectors name, type of analysis needed); theinformation has to be cross-referenced with thefield notebook and thesample collection sheets. Specific points of interest will be discussed below. In thenext sections we will discuss sampling of thevarious types of water. 10.1.3. Precipitation Thesampling strategy for rain and snow is in general dictated by thescientific aim of theprogramme. For example, thesampling interval may be monthly, weekly, daily, or even each hour. In all cases it is necessary to record theamount of precipitation so that weighted means of isotopic compositions can be calculated afterwards. Of course, themaximum information and least risk of evaporation results from short-term collection of precipitation. Samples should be stored individually in bottles. If only monthly mean compositions are required, daily samples can be combined in alarger storage bottle. For samples that are collected on weekly or monthly basis, theisotopic composition of thesample is likely to be modified by evaporation. This can be minimised by aspecial construction of therain gauge, or by placing asmall amount of mineral oil (2mm minimum) in thecollection bottle which is floating on thewater. Special care is to be taken when collecting snow. They should be allowed to melt slowly at ambient air temperature, avoiding evaporation. 10.1.4. Surface water Generally, thecollection method for surface waters pose few problems, when collected in relatively small quantity. Special care has to be taken when collecting water for carbon isotopic analysis. Field measurement of temperature, pH and salinity (especially with marine and brackish water) are needed. Thesamples are to be stored in glass bottles, in thedark, preferably at low 100

temperature, and should be poisoned by I2+KI or HgCl2. Thepoisoning recipes are: I2+KI solution: to be prepared by dissolving 15mg of I2 and 30mg of KI per mL of (ultra)pure water; water is poisoned by adding 0.5mL of this solution per L of sample HgCl2 solution: to be prepared by dissolving 70mg HgCl2 per mL of (ultra)pure water; 3mL of this solution is to be added per L of water sample. River and stream samples should be taken from mid-stream or a flowing part of the stream. Standing water near stream banks should be avoided as thewater may not be well mixed and show effects due to evaporation or pollution. Samples from lakes and estuaries should be collected from both thesurface and from depth. Together with other physical and chemical information, it may be possible to interpret theresults in terms of thewater-column structure. Care should be taken when sampling near aconfluence. For aconsiderable distance downstream of aconfluence, theriver samples may still show variable isotopic compositions due to incomplete mixing between thetwo different river waters. In large river systems this may amount to adistance of many tens of kilometres. 10.1.5. Unsaturated zone water Theisotopic profile of soil moisture can provide information on groundwater recharge. Samples are often taken from thesoil as such. Themost common methods to extract water from thesoil profile in the laboratory are (i) vacuum distillation, (ii) freeze drying, (iii) squeezing, and (iv) centrifugation. 10.1.6. Groundwater For all groundwater sampling, it is necessary to characterise as far as possible thehydrogeological situation (geophysical, geochemical, etc.) of theborehole. Pumped boreholes and production wells present little problem with thesample readily collected from thesurface supply. This is specifically true for thelarge quantity samples for conventional 14 C analysis (see Chapter 11). Sampling observation wells and especially very deep aquifers may pose more problems. First one should be aware

Water sampling and laboratory treatment

that standing water in such passive boreholes in theisotopic composition, or only changes that may not be representative for thewater mass in are accurately known. Water Sample Treatment theaquifer, because of evaporation or carbon diWater Sample Treatment oxide exchange with theambient air. It is usual to 10.2.1. The18O/16O analysis of water pump theborehole until it is purged by approxi(such as dissolved carbonic acid) are to be converted into a chemical compo as dissolved carbonic acid) are to be converted into a chemical comp mately twice thewell volume, or until(such steady used in the equipment. The specific requirement is that during this conversion used in the 10.2.1.1. equipment. The specific with requirement ismass that during this conversio state chemical conditions (pH, Eh) are obtained. Equilibration CO2 for introduced in the isotopic composition, or only changes that are accurately kn While this is common practice, it should be borne introduced in the isotopic composition, or only changes that are accurately kn spectrometric measurement in mind that in certain situations, thecone of deSince18 water poses many problems in mass pression resulting from pumping may 10.2.1 draw in THE O/16 O ANALYSIS OF WATER 18 16 O/ O ANALYSIS OF WATER 10.2.1 THE spectrometers primarily because of theadhewater from other sources. sion to metal, causing serious memory effectsIt may be practically impossible to collect suf- E 18 10.2.1.1 QUILIBRATION CO2 FOR MASS SPECTROMETRIC MEASURE O/16O ratio WITH of thewater sample has to be the 14 WITH CO2 FOR MASS SPECTROMETRIC MEASUR 10.2.1.1 EQUILIBRATION Treatment des Echantillons dEau C ficient water from a deep well for routine transferred to amore suitable gas, such as carbon Since water poses many problems in mass spectrometers primarily because analysis. In that case one has to turn to theAMS Themost common sample preparation Since waterdioxide. poses many problems in mass spectrometers primarily because 18 16 technique for which 250mL of sample is gener18 to metal, causing serious memory effectsthe O/ O ratio of the water s 18 16 de lchantillon deau doit tre transfr un gaz plus adapt, comme le dioxyde carb in water is theCO methodserious for memory 2 H 2O equilito metal, causing effectsthe O/ O ratio of the water s ally sufficient. 18 transferred tolaa more suitable gas, such asest carbon dioxide. The most c bration in which about amillimole amount of dans leau lquilibration CO H O dans de prparation plus classique pour transferred to a more 18 suitable gas, such as carbon dioxide. 2 The 2 most (10 to 20mL) is brought into isotopic equiCO une milli mole de (10 estis amene 2lquilibre avec quelques de l 2 CO2 20 in mL) water the CO H2O equilibration inmL which a preparation method for in water is the CO O equilibration in which a preparation librium methodwith for 18 2 H2 afew mL of sample water (generally 10.1.7. Geothermal water (gnralement 25,0 0,2C): amount of CO2 (10 to 20 mL) is brought into isotopic equilibrium with a fe 20 mL) is brought into isotopic equilibrium with a fe amount of CO 2 (10 at 25.0 to 0.2C): Both steam and liquid phases should be collected water (generally at 25.0 0.2 ooC): (generally 18 at 25.0 0.2 C):16 from geothermal fields so that the ratiowater steam/ H 2 O + C16 O 2 H 2 O + C18 O16 O water can be determined. This is relatively easy 18 16 H 2 18 O + C16 Otheequilibrated H 2 16O + C18 O16 16 18 16O then trans2 An aliquot of CO in production plants, but difficult in non-devel2 is H O + C O H O + C O 2 2 2 transfre au spectromtre de mass Une fraction aliquote de CO2 quilibr est ensuiteO ferred to themass spectrometer for 18O/16O meaoped geothermal regions. Thesteam is to be 18 con16 18 16 de CO est diffrent de celui de H2O (voir P de O/ O. Comme le rapport O/ O 18 16 2 densed, taking care that this procedure operates O/ O ratio in CO2 surement. Because the An aliquot of the equilibrated CO then transferred toand the mass spectrom 2 is 18 18 transferred to of the mass spectrom An aliquot of the equilibrated 2 is then la valeur de 18(see CO obtenue devrait tre corrige pour ce fractionne valeur de g/l) 16 quantitatively. O is different Sect.7.2.2 for thevalue H 2 Because the 18 measurement. O/ 16O ratio in CO2 and H2O is different (see S 18 18 measurement. Because O/obtained O international ratio has in CO and H2O is different (see S lchantillon etle standard de rfrence (voir Part.7.2.3) sont traits de l the value to 2 be corrected g/l) the Particularly critical for thermal waters is theneed g/l ) the 18 value obtained has to be corrected for this fraction value of 18 18 18 (i.e. quantits quivalentes deau et de dioxyde de carbone et mme temprature), for However. and inter- for this fraction of thefractionation. value obtained hassample to be corrected g/l)this to identify thesource of thespring and tovalue sample sample and international reference material (see Sect.7.2.3) treated eq correction nest pas ncessaire (Part.4.3.2): national reference material (see Sect.7.2.3) are are sample and international reference material (see Sect.7.2.3) are treated eq as close to thespring as possible. amounts of treated water and carbon and equal so that the c equally (i.e.dioxide equal amounts of temperature), water and amounts of water and carbon dioxide and equal temperature), so that the 18 18 18 carbon dioxide and relevant (Sect.4.3.2): RH 2O equal temperature), g / l RH 2Oso that 18 relevant (Sect.4.3.2): 10.2. Laboratory treatment of 1 = (Sect.4.3.2): 1 (water) = 18 thecorrection is not relevant 18 18 R R VSMOW / VSMOW g l water samples 18 18 18 18R 18 18 R HR O g / l 18RH 2 O 18 2 CO in equil . with H Theaim of this section is to offer thehydrologist RH O 18 1 2 1 = 2O g / l H2O 18 ( water ) = 18 (equilibra ted CO 2 ) 18 1 = 2 18 ( water ) = = 1 = 18 1 18RVSMOW 18RVSMOW some insight in theprocedures used by theiso18 R / g l CO 2 in equil . with VSMOW RVSMOW g / l RVSMOW tope laboratory to determine theisotopic com18 18RCO in equil.with H 2 O positions of thewater samples he sent/brought = 18 RCO22 in equil.with 1 = 18 (equilibrated CO 2 ) 18 H 2 O du CO quilibr avec ed lchantillon deau est quiva En dautres termes, la valeur = 1 = 18 (equilibrat CO 2 ) 18RCO 2 in equil. with VSMOW 2 to thelaboratory. Thepurpose is not to provide R 18 18 CO 2 in equil. with VSMOW de leau elle-mme, lorsque les valeurs de se rfrent la rfrence internationa thelaboratory detailed recipes for carrying out doit cependant souligner que les valeurs doivent tre corriges pour lquilibration e theanalyses. For that thereader is referred to (10.1) in other words the 18 value for CO2 equilibrated with the water sample is 18 IAEA Guidelines or specific laboratorys opera - words in other the value for with the water sample is lEq. 10.3, cause du terme additif deCO lEq. 10.2. 2 equilibrated 18 for CO equilibrated value in other words the18 value of the water itself, where the values 2 refer to the international refe 18 tion manuals and literature. Theprocedures will value of the water itself, exprimentaux where theis equal suivant values refer international 18 to the Les dtails et les indications cette mthode. refe value thewater sample tosappliquent the be discussed on thebasis of thevarious isotopes. We have to with emphasise, however, that the 18values do have to be corrected fo We have toof emphasise, that the values dorefer haveto to be corrected fo values thewaterhowever, itself, where the et H2O la Au cours according de lchange des atomes doxygne entre equilibration to isotopique Eq.10.3, because of the additive termCO in 2Eq.10.2. Nearly all isotopic measurement techniques theinternational reference VSMOW. We have to equilibration according to Eq.10.3, because of the additive term in Eq.10.2. leau change; il faut donc faire une correction; en considrant le bilan de masse en can not be applied to water as such. Therefore, emphasise, however, that the values do have to method. The following experimental details and concerns apply to this theunderlying principle of all methodsThe is that following experimental and concerns apply to acthis method. be corrected for details thewater -CO 2 equilibration 18 thewater or theconstituents to be analysed R 18 18 18 (such During cording the18isotopic exchange of the oxygen atoms and c between to Eq.10.3, because of theadditive term w R + c R = w R + c R = w + c 18 RcCO During the isotopic exchange of the oxygen atoms between CO22 and w0 c0 w c 0 0 18 as dissolved carbonic acid) are to be converted Eq.10.2. of the water changes; for this ca/ wcorrection has to b isotopicin composition into achemical compound that can be used in isotopic composition of the water changes; for this a correction has to b 18 O mass balance consideration we derive: 18 Thefollowing experimental details and concerns the equipment. The specific requirement is that O mass balance consideration ween derive: o w et c , et w et c sont les quantits mole des atomes doxygne dans leau e 0 0 apply to this method. during this conversion no changes are introduced 101 est: et c = c0, et en crivant = c/w, la valeur corrige du CO2 quilibr
18

carbone respectivement avant et aprs lquilibration, et le facteur de fractionn

gal 1 + 18g/l tel que dfini dans le Tableau 7.4 (gnralement 25C); en supp

c/w18Rw0 = 18Rc(1 + 18c/w) 18c/w18Rc0

g /l

VSMOW 18

RCO 2 in equil . with VSMOW

(10.1)

in equil . with H 2 O

n equil . with VSMOW 18

2 En dautres termes, la valeur 18 du CO 2 quilibr avec lchantillon deau est quivalente la valeur

1 = (equilibrated CO )

de leau elle-mme, lorsque les valeurs de 18 se rfrent la rfrence internationale VSMOW. On

INTRODUCTION

doit cependant souligner que les valeurs doivent tre corriges pour lquilibration eau- CO2 suivant CO2 quilibr avec lchantillon deau est quivalente la valeur lEq. 10.3, cause du terme additif de lEq. 10.2. aleurs de 18 se rfrent la rfrence internationale VSMOW. On abundant. Otherwise adrop of concentrated During theisotopic exchange of theoxygen Les dtails et les indications sappliquent cette mthode. eurs doivent tre corriges pour exprimentaux lquilibration suivant eau- CO 2 suivant

3 4 de lEq. composition ofdes thewater changes; entre for CO2 et H2O la composition de 10.2. Au cours detopic lchange isotopique atomes doxygne deTheequilibration technique this acorrection hascorrection; to be made; from an 18O leau change; il faut donc mthode. faire une en considrant le bilan masse en 18O on obtient: mentaux suivant sappliquent cette

atoms between CO2 and H2O theoxygen iso-

H PO may be added.

que des atomes doxygne entre CO2 et H2O la composition de 18 Rc 18 18 18 une correction; en considrant en+ O on w0 18 Rw0 + le c 0bilan Rc 0de =masse w 18 Rw c Rcobtient: =w
18

mass balance consideration we derive:

c/w

18 Rc w 18 Rw +o c 18 R = w + c 18 Rc quantits en mole des atomes doxygne dans leau et de di oxyde de c w0 et c0, et 18 w et c sont les

determines theoxygen isotopic activity rather than concentration of thesample. Therefore, in saline + c 18 Rc waters and brines it is required to determine thechemistry of thesample.

in water. There are other methods which are in an (10.2) experimental stage or specifically applicable to in Table7.4 (commonly at 25C); assuming certain problems. These will only briefly be menEn termes de valeurs de ceci conduit and une valeur corrige de 18 de: that w = w and c = c , writing = c/w, 18 18 0 0 c/w) c/w Rc0 (10.2) tioned. thecorrected value of theequilibrated CO2 is: 18 18 18 18 c' = (1 + 1818 (1) Water can be (10.3) converted quantitatively to O2 c/w ) c c/w c0 18 corrige 18 de: 18 18 18 conduit une valeur de c/w Rw0 = Rc(1 + c/w) c/w18Rc0 (10.2) by fluorination with bromiumpentafluoride: In terms of values this comes(10.3) to acorrected 18c/w 18c0 171 + 2HBr + 3O2 (2) 6H2O + 2BrF5 9HF 18 value of: (3) Theoxygen released can be isotopically ana18 c = (1 + 18c/w )18c 18c/w 18c0 (10.3) 171 lysed directly or is reacted with hot graphite to produce CO2 for mass spectrometric Automated units can be procured with either analysis [105]. Theadvantage of this method an air bath or water bath. Theformer are easier to operate, but thelatter show abetter temis that only 9mg of water is needed. Thedisperature stability and homogeneity throughadvantage is that BrF5 is an extremely danout thebath. gerous liquid and needs extended laboratory Avariation in equilibration temperature of installations and precautions. 1C causes an uncertainty in the18c value of (4) Water can be reacted in nickel tubes with 0.2. Therefore, the temporal variation of thebath should generally be much less than graphite at high temperature to produce 0.5C, preferably no more than 0.2C. CO2 [106]. Theequilibration time depends on theampli(5) The 18O/16O and 17O/16O ratios of water can tude and frequency of shaking and theamount be determined by analysing O2mass spectroof sample. Typical equilibration times are in metrically that is produced by electrolysis of theorder of 4 to 8 hours. water. Theprecision obtained is about 0.1; In order to remove oxygen and other gases theadvantage especially concerns thedirect from thewater sample prior to equilibrameasurement of 17O which is problematic tion two ways are being used: (i) freezin CO2, as the13C containing molecule has ing thesample and removing thegases by pumping (repeated procedure), (ii) pumpthesame mass and is much more abundant ing thewater sample at ambient temperature [27]. through acapillary, so minimising theevapo(6) Apromising new method is measuring isoration (and consequently isotope fractionation) of thesample. tope ratios (2H/1H, 17O/16O, 18O/16O) in water directly by laser absorption spectroscopy ThepH of thewater needs to be in therange of 6 to 7 so that dissolved CO2 and HCO! are [25]. 102

w dfini and dans c0, and w and 7.4 c are themole 25C); en supposant que w = w0 le Tableau (gnralement gal 1 + 18where g/l tel que 0 Equilibrating CO2 with thewater sample is antits en mole des atomes doxygne dans leau et de di oxyde de and amounts of oxygen atoms in thewater et c = c0, et en crivant = c/w, la valeur corrige 18 du CO2 quilibr est: themost common method for measuring 18O/16O c/w est et aprs lquilibration, et le facteur de before fractionnement carbon dioxide and after theequili-

18 10.2.1.2. Other methods c/w est carbone respectivement avant et aprs lquilibration, et le facteur de fractionnement

c/w

ns le Tableau 7.4 (gnralement 25C); en supposant que bration,18 respectively, and thefractionation 18 18 w = w0 c/w18Rw0 =18 Rc(1 + 18c/w) 18c/w 18 Rc0 factor is equal to 1 + g/l as defined c/w est: la valeur corrige du CO2 quilibr

Water sampling and laboratory treatment

10.2.2. The2H/1H analysis of water 10.2.2.1. Reduction of water to H2 for mass spectrometric analysis

(2) measuring the3H activity by proportional gas counting (PGC) (3) measuring theamount of daughter 3He mass spectrometrically after storing thesampling for a specific time in the laboratory (Sect.12.1.5.2).

10.2.2 10.2.2.1

The first method is generally carried out as ZnO + in H2 steel 500C H abatch process tubes. In thesecond 2O + Zn Therange of choices is extra broad by thecommethod theevaporated sample is running through bination of (1), (2), or (3) with either (a) or (b). ou 2H2O + U UO2 + 2H2 800C afurnace containing uranium turnings. Both opThechoices to be made will be discussed in La premire tions mthode seffectue de manire groupe avec des tubes en acier. Dans la we seconde Chapter 11. Here will restrict ourselves to require about 10mL of water. Although aplchantillon plying vaporuranium est traithas dans un four contenant des copeaux duranium. Les deux options thedifferent chemical/physical procedures. less experimental complicancessitent environ 10 L deau. Bien que mthode soit plus simple exprimentalement, tions, thedisadvantages arelathat it is uranium poisonous TheLSS technique is being applied to water itelle prsente and les dsavantages de la luranium dune plus grande difficult lobtenir etto be mixed with apropmore difficult totoxicit obtain de and dispose et of. self. Thesample then has sen dbarrasser. er scintillation liquid (Chapter 11). PGC requires asuitable gas, as thestable isotopic analyses. 10.2.2.2. Other methods 10.2.2.2 AUTRES METHODES Similar to theequilibration method for 18O/16O 18 Water 2 purification 2 1 Comme pouranalysis, la mthode par utilise sample pour lanalyse O/16O, le rapport H/1H dun H/quilibration H ratio of awater can bede 10.2.3.1. the isotopique et al., 1991): collected contains too many conchantillon deau peut tre transfr H2 par change exchange [107]: (Coplen transferred to H2 by isotopic Often thewater taminants to allow direct LSS measurement as 2 1 H HO + 1H 2 1H 2 O + 2 H1H well as electrolytic enrichment. Especially coloured contaminants hamper aproper liquid scinComme pourAs les in ractions chimiques, la technique dquilibration plus lie aux activits quaux chemical reactions, theequilibration tech- est tillation performance. Purification of water is carconcentrations. En consquence, chimie de leau doit tre than connue. ried Il y out a dautres inconvnients nique is concerned la with theactivities rather by distillation . As amatter of fact, most concentrations. Consequently, thechemistry of comme le fait que cette mthode ncessite un investissement relativement important et un contrle de laboratories routinely subject all water samples thewater sample ismesure to be known. Other disadvanla temprature trs prcis dans la o le fractionnement varie fortement avec les Therequirement modifications to distillation. is that no isotopic tages are that themethod needs arelatively large change occurs during this treatment. Therefore, de la temprature (6 par C). Lavantage est que cette procdure est plus rapide. investment and that avery good temperature conthedistillation procedure has to be as quantitatrol is needed, as3 theisotope fractionation varies tive as possible, i.e. ayield close to 90%. Also 10.2.3 LANALYSE DU H DE LEAU considerably with theexchange temperature (6 thewater sample should hardly be in contact with theambient of which thevapour content may C). Theadvantage is that theprocedure is per Pour mesurer la oconcentration en tritium de leau il existe plusieurs options. Le air, choix doit tre 3 H content of thesample through exaffect the faster than theother techniques. dtermin par la concentration (attendue) de lchantillon et la prcision souhaite. Les diffrentes change, which is an extremely fast process. procdures de traitement sont :
3 H analysis water liquide (SSL) The (1) mesurer 10.2.3. lactivit en H par spectromtrieof scintillation

Encore une fois, lintroduction deau dans le spectromtre de masse doit tre vite. Cest pourquoi, le ZnO + H2 at 500C H 2O + Zn rapport 2H/1H est gnralement transfr un gaz mieux adapt, dans ce cas lhydrogne. La (a) treating thesample as it is collected est gnralement ralise en rduisant leau sous plusieurs centaines de degrs avec production de H 2 or 2H2O + U UO2 + 2H2 at 800C (b) treating the sample after artificial enrichdu zinc ou de luranium (appauvri): ment.

Again theintroduction of water themassdEau specTreatment desin Echantillons 2 trometer has to be avoided. Therefore, the H/1H ratio is commonly transferred to amore suitable Moreover, thepossibility exists to increase LANALYSE DE 2H/1H DE LEAU gas, in casu hydrogen. Theproduction of H2gas theoriginal 3H content artificially (i.e. to enrich) is generally performed by reducing thewater at by aknown amount, usually through electrolysis, several hundred C or (depleted) R EDUCTION DE Ldegrees EAU EN H POURzinc LANALYSE AU SPECTROMETRE DE MASSE 3 2 with prior to the H measurement. Therefore, theaduranium: ditional options are:

measuring thetritium content of water sevcomptage proportionnel du gaz (CPG) (2) mesurer For lactivit en 3H par eral options exist. Thechoice is to be determined

10.2.3.2. 3H enrichment Two methods exist for theartificial enrichment of

3 procedures are: Par ailleurs il est possible daugmenter artificiellement la concentration enThermal H (i.e. enrichir) dune (2) diffusion of H2 prepared by re3 H. Ainsi les options quantit connue, habituellement par lectrolyse , avant de mesurer le duction activity by liquid scintilla (1) measuring the3H of water using, for instance, zinc supplmentaires sont : spectrometry (LSS) or magnesium. By this method very high tion

3 3 (3) mesurer by parthe(expected) spectromtrie de stock lchantillon au 3 masse la quantit d He fils aprs avoir H in water: H content of thesample and laboratoire pendant une dure donne (Sect. 12.1.5.2). theprecision required. Thedifferent treatment (1) Electrolysis of thewater sample

(a) Traiter lchantillon au moment du prlvement, (b) traiter lchantillon aprs enrichissement artificiel. 173

103

INTRODUCTION

enrichment factors can be obtained, but theequipment and sample handling is complicated. It is not in use in common laboratories. Theprinciple of thermal diffusion is that, when agas mixture is in contact with acold wall as well as ahot wall, thehighmass (isotopically heavy) component tends to concentrate in thecold and thelow-mass (isotopically light) component in thehot region. If this principle is applied to avertical, double-wall tube structure in which theinner tube is heated and theouter wall is cooled, theheavy component concentrates at thecold wall and then, having ahigher density (at low temperature) moves downward and concentrates at thelower end of thetubes. Thehot and light component concentrates at thetop volume. Consequently, aseparation of the(isotopically) heavy and light molecules, in this case 3H1H and 1H2 respectively, is obtained. The first method is relatively simple, requires little sample handling and supervision during enrichment, and can be applied simultaneously to aseries of samples including reference samples. During electrolysis the purified sample (sect.10.2.3.1) is provided with Na2O or 3H-free NaOH to increase theelectrical conductivity and subsequently decomposed by an electric current: 2H2O 2H2 + O2 Thehydrogen isotope fractionation is remarkably large (contrary to theoxygen isotope fractionation): about 90% of the3H content of theoriginal water sample remains in thewater (theescaping H2gas is very much depleted in 3H). This means that, if aquantity of water is condensated by afactor of 10, theenrichment is about 9. After electrolysis theenriched sample, now containing alarge concentration of NaOH, is again to be distilled to remove theconcentrated electrolyte prior to activity measurement. Depending on themeasurement technique to be applied, an amount of water is needed of 5 to 20mL. If thesample is to be enriched, thedesired quantity is 250mL (see Table10.2). 10.2.3.3. Preparation of gas for PGC of H
3

(1) hydrogen, prepared by H2O + Zn or Mg ZnO + H2 thehydrogen gas prepared has to be mixed with aproper counting gas such as argon (2) ethane or propane, prepared by theaddition of hydrogen made as under 1) to unsaturated hydrocarbon: C2H4 + H2 C2H6 C3H6 + H2 C3H8 (with Pd catalyst) (with Pd catalyst)

which are suitable counting gases as such. Theadditive reactions given under (2) expire at elevated temperatures in thepresence of asuitable catalyst. 10.2.4. The14C analysis of dissolved inorganic carbon 10.2.4.1. In thefield In natural waters theinorganic carbon content plays an important role. As we have seen in preceding chapters, thetotal dissolved inorganic carbon (DIC) consists of varying concentrations of carbonic acid (H2CO3 or rather dissolved CO2), dissolved bicarbonate (HCO!), and dissolved carbonate (CO$). There are two methods in use for obtaining theDIC fraction in water for measuring the 14C content or the13C/12C ratio. Both, however, collect thetotal amount of DIC (for unravelling theseparate 13 values of thecomponents we have to use theprocedures discussed in Chapter 9): (1) Addition of acid and extracting thegaseous CO2 formed: aCO2(aq) + bHCO!+ cCO$ + (b + 2c)H+ (a + b + c)CO2 + ...H2O Special, simple to operate, equipment takes care that theescaping CO2 is dissolved in asmall amount of alkaline solution in aplastic bottle and shipped to thelaboratory. (2) Precipitating DIC as BaCO3 after adding NaOH solution: aCO2(aq) + bHCCO$ + cCO$ + (2a + b)OH (a + b + c)CCO$ + ...H2O (a + b + c)CO$ + BaCl2 (a + b + c) BaCO3 + ...Cl

For proportional gas counting (Sect.11.3.1) of 3H afew gases are suitable: 104

Water sampling and laboratory treatment

Also here theequipment (provided by thelaboratory) is simple: theprecipitate is collected in asmall plastic bottle and shipped to thelaboratory. Both procedures are to be carried out in thefield, to avoid having to transport alarge quantity of water to thelaboratory. Depending on theDIC content of thewater, for theconventional 14C analysis between 25 and 50L is required. With theintroduction of theAMS technique this problem no longer exists, as for this method only afew mg of carbon is needed. Thesame is valid for 13C/12C analysis. This means that aquantity of 250 mL of water is generally sufficient for both carbon analyses. Additionally, no treatment is required in the field. The 13C sample, however, needs careful storage (sect.10.1.4). 10.2.4.2. In thelabo0ratory In principle theprocedures for treating thevarious samples received from collection in thefield are analogous: treatment with acid (generally HCl solution) and purification of the escaping CO2. Subsequently different methods are to be applied, depending on the14C measurement technique, in chronological order of first application: (1) activity measurement in aproportional gas counter (PGC) as CO2, C2H2, C2H6, or CH4 (a) if CO2 is used in thegas counter directly, it has to be extremely pure; this purification is themain effort of thesample treatment by thelaboratory (b) preparing acetylene from CO2 is performed in 2 steps: 2CO2 + 9Li 4Li2O + Li2C2 (700C) Li2C2 + 4LiO2 + 6H2O 4Li(OH) + C2H2 (c) preparing ethane from theacetylene prepared as under b) C2H2 + 2H2 C2H6 (with Pd catalyst) (d) preparing methane from CO2: CO2 + 4H2 2H2O + CH4 (300C + Ru catalyst)

(2) activity measurement in aliquid scintillation spectrometer (LSS) as C6H6 theacetylene gas prepared under 1b) can be condensed to benzene: C2H2 C6H6 (with catalyst) thethus formed benzene is to be mixed with aproper scintillation fluid (Chapt.10). (3) concentration measurement in an accelerator mass spectrometer (AMS) as graphite or CO2; in thepresence of iron catalyst, CO2 is reduced to graphite: CO2 + 2H2 2H2O + C (at 600C with Fe) thegraphite is directly transferred to theaccelerator target (see Chapter 10). 10.2.5. The13C/12C analysis of dissolved inorganic carbon This procedure has been discussed in sect.10.2.4.2, as it is similar and in fact it runs paralle to the14C procedure. TheCO2 extraction can be carried out by acidifying thewater sample and collecting theevading CO2 during vacuum pumping. Thesample can also be flushed with aclean gas, such as nitrogen or argon, and theevading CO2 likewise condensed in acold trap. One concern with these samples is that thewater is likely to exchange with theatmosphere, if it is not completely sealed of. 13C/12C then changes to ultimately isotopic equilibrium with atmospheric CO2. Parallel thepH of thewater changes to higher values. Thesample should therefore be stored in aglass bottle and sealed properly. Thesecond concern is theingrowth of organic matter in thewater sample. As this has a13 value much smaller that theDIC, thelatter will increase. In order to avoid this process, thesample is to be stored at low temperature in thedark, preferably after poisoning (sect.10.1.4).

105

11. measuring techniques

11

Theaim of this chapter is to give some insight in thevarious existing techniques for measuring A TECHNIQUES DE MESURES M a g n e t i c eld isotope ratios and radioactivities. Thepotential readers are thehydrologists which apply theiso15 to 50 cm tope techniques and their students assisting in Ion thelaboratory on theone hand, and starting labocollectors ratory technicians receiving afirst glance of their Positive ions low hi h Le but de cefuture chapitre est de quelques informations sur les diverses techniques work, ondonner theother. Thereview is general High voltage E utilises mass mass chamber pour mesurer et dethemethodologila radioactivit. Les lecteurs Ionisation concerns sont les in des thisrapports respect,isotopiques that it covers Gas ow cal field, although laboratories often do not have hydrologues qui appliquent les techniques isotopiques et leurs tudiants qui les assistent dans Ion source all techniques at their disposal. Technical details leur laboratoire; il sagit aussi des techniciens dbutant qui peuvent recevoir ainsi un premier m q vary among laboratories and manufacturers. v B aperu de leurs travaux futurs. De ce point de vue, la prsentation sera donc gnrale, de F r Therefore, we restrict ourselves to theunderlying manire couvrir le volet mthodologique, et ceci, bien que les laboratoires naient pas principles. B toujours toutes les techniques leur disposition. Les dtails techniques varient suivant les laboratoires et les constructeurs. Cest pourquoi nous allons nous restreindre aux principes 11.1. Mass spectrometry for gnraux noncs ci-dessous. Fig. 11.1. Schematic view of mass separation in stable isotopes
+

sation chamber and accelerated in the ion source by their relative abundances. This principle is shown a high voltage E. In a magnetic field perpendicular 11.1.1 PRINCIPE PHYSIQUE in Fig.11.1A where thegas containing different to thesurface of this paper theisotopically light and 12 13 isotopes of an element ( C and C in CO2, for Un spectromtre de masse est capable de sparer des atomes ou des ions ions de masses diffrentes heavy are separated and collected by collectors. instance) is ionised in theion source. TheposiThis results in electrical currents et de mesurer leurs abondances relatives. principe est indiqu sur la Fig. 11.1A o un gaz that can be measured tive ions are accelerated byCe high voltage and 12 13 very precisely. contenant diffrents isotopes dun lment (field C et C du CO subsequently enter a magnetic perpendicu - 2, par exemple) est ionis dans B.tension Representation of ensuite the Lorentz force: a charged lar to the electric field (in fig.11.1A drawn in une source dions. Les ions positifs sont acclrs par une haute et entrent particle with positive electric thesurface of this paper). Thepath of theions dans un champ magntique perpendiculaire au champ lectrique (sur la Fig. 11.1A reprsent charge q+ and mass m moves in a flat surface with a speed v in a magnetic now becomes circular because of theLorentz par la surface du papier). La trajectoire des ions devient alors circulaire de par la force de surface; the resulting field B perpendicular to that force (Fig.11.1B). Thecircle radius depends on Lorentz (Fig. 11.1B). Le rayon du cercle dpend de la masse de lion: les ions les plus lourds Lorentz force F is perpendicular to B and v and causes theion mass: theions with heavier masses follow theparticle to follow acircular suivront un thelarger cercle plus grand. De cette faon, les ions se sparent et peuvent donc tre path with radius r. circle. In this way thedifferent isotocollects. Dans les collecteurs, les ionsand perdent leur charge lectrique, produisant ainsi de pic ions become separated can be collected. Techniques de Mesure is due to In these collectors theions loose their electric Techniques de acceleration Mesure faibles courants lectriques qui peuvent tre mesurs (Fig. 11.2). Thevelocity of theparticle charge, causing small electric currents that can be by thehigh voltage in theion source (Fig.11.1B): La magnitude de la force de Lorentz est: measured (Fig.11.2). 1 2 E = 1 mv 2 = qV (11.3) E kin kin = 2 mv = qV Themagnitude of theLorentz force F is: 2 F q v (11.1) = B From Eq. 11.2 and 11.3 follows theradius of (11.1) F = Bq v Des Eq. Eq. 11.2 11.2 et et 11.3 11.3 on on dduit dduit le le rayon rayon de de la la trajectoire trajectoire circulaire circulaire des des diffrents diffrents Des thecircular path of thedifferent isotopic ions: Cette force est gale la force centripte ncessaire pour garder la particule sur une trajectoire This force is equal to thecentripetal force recirculaire : quired for keeping theparticle in thecircular 2 2V V/ /q q 1 2 mV r= = 1 2 mV = = m m r path: (11.4) B q B B q B 2 mv (11.2) F= = Bqv (11.2) r 19 o q est est gal gal la la charge charge de de llectron llectron = = 1,6 1,6 10 1019C C et et B B et et V V dpendent dpendent des des o q 179 linstrument. Pendant la mesure, le voltage lectrique et le champ magntiq linstrument. Pendant la mesure, le voltage lectrique et le champ magntiq constants, constants, de de telle telle faon faon que que le le rayon rayon est est proportionnel proportionnel la la racine racine carre carre de de la la r (:) (:) m m. . La La diffrenciation diffrenciation (d (dr r/d /dm m conduisant conduisant lapproximation lapproximation r r/ / m m) ) donn donn r

A.ISOTOPES The gas containing isotopic molecules enters 11.1 SPECTROMETRIE DE MASSE POUR LES the ion source and is ionised by electron bombardAmass spectrometer is able to separate atoms STABLES ment. The positive ions are extracted from the ionior rather ions with different mass and measure

11.1.1. Physical principle

amass spectrometer.

r / r

2V / q

2V / q

E kin =

1 2 mv = qV 2

(11.3) Des Eq. 11.2 et 11.3 on dduit le rayon de la trajectoire circulaire des diffrents i

Des Eq. 11.2 et 11.3 on dduit le rayon de la trajectoire circulaire des diffrents ions: 2V / q 1 2 mV INTRODUCTION m r= = B B q 2V / q 1 2 mV m r= = (11.4) B to carbon dioxide, being representative for 2- and where is equal theelectron B q 19 on charge=1.610 C and B and V depend gases. gal 3-atomic la charge de llectron = 1,6 1019C et B et V dpendent des p o q est theinstrument settings. During ameasurement linstrument. Pendant la mesure, le voltage lectrique et le champ magntiqu la charge voltage de llectron 1,6magnetic 1019C et B et V dpendent des paramtres de o q est gal the electric and = the field are constants, de 11.2.1. telle faon que le rayon est proportionnel la racine carre de la m Measurement of 2H/1H inH 2 kept constant, so that theradius is proportionlinstrument. Pendant la mesure, le voltage lectrique et le champ magntique sont gards (:) m . La diffrenciation (d r/d m conduisant lapproximation altelle to thesquare root of est theion mass: rr Thecase of hydrogen is complicated by thefact r/m) donne: constants, de faon que le rayon proportionnel la racine carre de la masse de lion: Differentiation (dr/dm leading to theapproximathat in theion source H2gas combines with ahyr (:) m . La diffrenciation (dr/d m conduisant lapproximation r / ) donne: 2 2V / q <3>. tion r/m) results in: V / q 1H+ rm /r also drogen to form and r / r 3 which =ion m / m = has mass from m m B B / Thenecessary correction is obtained an ex 2V / q 2V / q r / r = and m / m = r / r (11.5) to ion source gas pressure trapolation procedure B m / m 1 mesure Cette quation est une de la rsolution du spectromtre de B dernire H+ equal zero where 3 disappears. (11.5) m = 1, m est la rsolution de si r est suffisamment grand pour p Theconstants c2linstrument and Cette dernire quation est une mesure de la rsolution du spectromtre de masse: pour c3 contains thepropordistinction claire entre les pics pour les masses m et m+1 dans le spectre gnral. tionality factors for une theionisation probabilities, m = 1, m est la rsolution de linstrument si r est suffisamment grand pour permettre Thelatter is ameasure of theresolution of the transmission and collection efficiencies of ont typiqueme themass formasses Dm=1, mm is theresoLes Spectromtres de Masse de Rapports Isotopiques (SMRI) distinction claire entrespectrometer: les pics pour les m et +1 dans le spectre gnral. with masses <2> and <3>. Because lution of theinstrument if Dr is large enough to (dethemolecules rsolution lordre de 100), contrairement aux spectromtres de masse org these factors are Les Spectromtres de Masse de Rapports Isotopiques (SMRI) ont typiquement de unequal faibles unity, theisotope ratios allow aclear distinction between thepeaks for ont des rsolutions de plus de 104. Toutefois ces derniers ont de plus faibles sen obtained from thecurrent masses m de and m+1contrairement in themass spectrum. rsolution (de lordre 100), aux spectromtres de masse organiques qui ratios have to be comsont donc pas adapts aux mesures des rapports isotopiques. pared to those of acommon (internationally Techniques de Mesure adont des rsolutions plus de 104.Spectrometers Toutefois ces derniers de plus faibles sensibilits et ne Isotopede Ratio Mass (IRMS)ont have opted (see Chapter 7)) standard: Techniques de Mesure typically lowmesures resolution (in theorder of 100), sont donc pas adapts aux des rapports isotopiques. + 2 11.2 DETERMINATION DES DABONDANC contrary to theorganic mass spectrometers (c3 / c 2 ) [RAPPORTS H1H + 1H 3 ] /[1 H ( I 3 / I 2 ) sample gas 2 ] sample gas Techniques de Mesure = with resolutions of more than 104. Thelatter, on + 2 1 1 1 + 2 1 1 1 ISOTOPES STABLES ( /I ) ( c33 // c c22 ) (c )[ [ H HH H+ + H H33 ] ]/[ /[ H H22 ] ] reference gas 11.2 DETERMINATION DES lower RAPPORTS DES I3 (I gas 3 / I2 2 )reference sample gas sample gas theother hand, have much sensitivity DABONDANCE and = 2 1 1 + 1 2 1 1 /+ 1 positifs are therefore not suitable for isotope( I ratio meaI 3(/cI (qui (c H+ H /[ H 2 ] reference Les faisceaux correspondent aux des molcules isotop ISOTOPES STABLES 2 ) reference gas 3 cions 2) [ H 3 ] diverses gas 3 / c 2 ) [ H H + H 3 ] /[ H 2 ] sample 3 / I 2 ) sample gas gas + surements. = (11.7) Aprs correction pour la participation de H et en insrant les rapport isotop (11.7) 3 + charge 2 1 1 la 1 vers(c les/ c collecteurs. L, lectrique est transfre au mtal d ( I 3 sont /diverses I 2 ) dirigs reference gas 3 isotopiques 2) [ H H + 3 ] /[ H 2 ] reference gas Les faisceaux qui correspondent aux ions positifs des molcules du H gaz 2 + value devient: de ce qui produit des courants lectriques (de I) dans les connections collecteurs Aprs correction pour la participation H3 et en insrant lesdes rapport isotopi sont dirigs vers les collecteurs. L, la charge lectrique est2transfre au mtal des collecteurs + 11.2. Reporting stable isotope partir rapport entre ces courants les isotopiques After correction for theH contribution and in- des gaz originels du value devient: de 3 rapports 2 de 1 Aprs correction pour la des participation H3+11.2). et en A insrant les ce qui produit desAbundance courants lectriques (I) dans les connections collecteurs (Fig. 0 rapport isotopiques, la valeur 2 ratios ( H/ H) ( I / I ) sample sample becomes: serting 2 3 2 value dtermins. Chaque courant est ratios, proportionnel (coefficient 2 originels = 2theisotopic 1 = the 1 c) la pression pa partir du rapport entre ces courants les des gaz value isotopiques devient: de rapports 1 peuvent tre 0 2 H/ 1H) 0 ( I / I ) ( reference Theion beams consisting of positivecompos ions ofdans2 le gaz.. ( H/ H)reference ( I3 / I2 ) sample sample dtermins. thevarious Chaque courant est proportionnel ) la pression deson = 2 partielle 1 1= 3 2 0 isotopic molecules in (coefficient thegas are cfo1 2 1 ( I 3 / I 2 ) reference ( H/ H) reference 0 + 1 12 16 ( H/ H) compos dans le gaz.. (]I 3 / I 2 ) + sample cussed in thecollectors. Here theelectric charge sample 2 I2 = c0 H I44 = cde C contribution O2+] 2[ 2 44[ la lexposant se rapporte la correction de H 3 la m = o = 1 (11.8) 1 2 1 0 (11.8) is transferred to themetal collectors, resulting ( I / I ) ( H/ H) reference reference 3 2 standards + + 1 + 13 16 16 ++ 0 [2pour valeurs absolues (chantillons de rfrence) seO + I3 = c Hrapporte H les + 1H I45 = c Ccontribution O2 + 12C17O 3 se 3 45[ la o ]la correction de de Htrouvent I c2[1H2+] currents (I) in thecollector I44 = c44[12C16O in connec3 ] la m 2 =electric 2 ] lexposant 11.2. absolues pour les standards (chantillons tions (Fig.11.2). theratios of these 12 18 +rfrence) valeurs de se 16 trouvent d + + 2 1 + 1 From 13 16 12 17 16 mass + 2 mass 3 0 currents mass mass 45 mass 46O+ + 13C17 I46 44 =c CH O16 O+ Les + 12C 46[ I I = c C O O ] correction (11.6) o lexposant se rapporte la de la contribution de la masse O <3>. 3 = c3[ H H + H3 ] 45 45[ C O 2 + 3 1 1 2 1 theisotopic ratios of theoriginal gases11.2. can be H H H H 12 16 12 18 16 C O2 C O O valeurs pour (chantillons de rfrence) trouvent dans le tableau 12 18 (coeffi 16 13 standards 12 17 14 15 determined. Each current is proportional 13 16 se 13 I46 = cabsolues O+ +les C17O16O+ + C O2+] MESURE DE N/ N DANS N C O 2 C 17O 16O 46[ C O11.2.2 2 mass 28 mass 29 12 17 16 cients c) to thepartial pressure 11.2. of therespective C O O 12C 17O 2 14 14 N N 15N 14 N 14 15 14 11.2.2 MESURE DE 15 N/ de N DANS Lanalyse au spectromtre masse N du N/ N des corps contenan 2 rapport component in thegas. 15 14 o dans ce cas leffet galement simple, peut encore plus, la mesure Lanalyse au masse du dans rapport N/ N des corps contenant 11.2.2 MESURE DE 15N/14 N spectromtre DANS N2trede + 1 1 + provoque, pour lhydrogne, la formation de H , nintervient pas. Les ra 3 I2 = c2[ H2 ] c o l l e c t o r s galement simple, peut tre encore 15 plus, 14 dans la mesure o dans ce cas leffet Lanalyse au spectromtre de masse du rapport N/ N des corps contenant de lazote est 181 + 1 mesurs sur le faisceau se traduisent de manire simple rapports isotopiques Ien 46 provoque, pour lhydrogne, la formation de H , nintervient pas. Les rap 3 ] I3 = c3[2H1H+ + 1H+ 3 galement simple, peut tre encore plus, Idans la mesure o dans ce cas leffet de pression qui I 3 or I 29 45 mesurs sur le faisceau se traduisent de manire simple en rapports isotopiques 1 provoque, pour lhydrogne,( I la formation de H3+ nintervient rapports ioniques I44 = c44[12C16O+ 2] I 44 /,c28 ([ 15 N14 N] /pas. [ 14 NLes ]) chantillo I 2 or n I 28 c 29 29 / I 28 ) chantillo 2 n = = 15 14 14 mesurs sur le faisceau se traduisent de manire simple en rapports isotopiques: + 12 17 16 15 14 14 ( / ) I I c / c ([ N N] / [ N ]) Fig. 11.2. The various isotopic ions of hydrogen and + C O O ] I45 = c45[13C16O+ 29/ I 28 rfrence 29/ c 28 2 rfrence 2 c ( I 29 ) ([ N N] / [ N ]) 28 chantillon 2 chantillon = 29 28 are carbon dioxide, respectively, in the col- = 15 focussed 14 14 17 + ( / ) I I c / c ([ N N] / [ N O ] I46 = c46[12C18O16O+ + 13C17O16O+ + 12C 15 14 14 29 28 rfrence 29 28 2 ]) rfrence 2I ) lectors (Faraday cups). These collect the electric c ( I 29 / 28 chantillon 29 / c 28 ([ N N] / [ N 2 ]) chantillon = = 15 14 are picked charges (electrons thepositive ions) ( 1514 N / 14up N) by ( I 29 / I(11.6) c29 / c chantillon 28 ) rfrence 28 ([ N N] / [ N 2 ]) rfrence = 15 +1 resulting in electric=currents for the various isotopic 15 14 15 N / 14 N) rfrence ( ( N / N) Theisotopic compositions can now be calculated. molecules. From theratios theisotopic ratios chantillo n = 15 of14these = 15 + 1 or N214 (left) and CO (right) can be deduced. We restrict ourselves to discussing hydrogen and of H215 ( 2N / N) rfrence ( N / N) chantillon 15 Le N2 de lair varie peu est choisi = qui = comme + 1 rfrence ou standard,:(11.9) ( 15 N / 14 N) rfrence Le N2 de lair 15 qui varie peu est choisi comme rfrence ou standard,: 108 R(N2 standard de lair) = 0,0036765

( (

( ( ( ) )

) ) )

Le N2 de lair qui varie peu est 15 choisi comme rfrence ou standard,: R(N2 standard de lair) = 0,0036765 La prcision de la spectromtrie de masse est denviron 0,02 . Toutefois, les 15 R(N2 standard de lair) = 0,0036765 (11.10)

measuring techniques

where thesuperscript 0 refers to thecorrection procedure for theH3+ contribution to mass <3> ions. Absolute values for thestandards (reference samples) are given in Table11.2. 11.2.2. Measurement of 15N/14N in N2 Themass spectrometric analysis of N2 for obtaining 15N/14N in nitrogen containing materials is equally simple, even more so, since in that case we have not thepressure effect in theion source that resulted in theformation of 1H3+ with hydrogen. Themeasured ion beam ratios are simply translated 15 into isotope ratios: c / c ([ N14 N] / [ 14 N 2 ])sample = 29 28 15 14 = 14 15 14 c(29 / c ([ N N ] / [ N ]) 28 2 reference I 29 / I 28 ) sample c29 / c28 ([ N N] / [ 14 N 2 ])sample = = ( I 29 / I 28 ) reference c29 / c28 ([ 15 N14 N] / [ 14 N 2 ]) reference

11.2.3. Measurement of 13C/12C and 18 O/16O in CO2 Themeasurement of theisotopic composition of CO2 is complicated by theabundance of molecules with equal mass <45> and <46>, containing different isotopes (Fig.11.2). From can deduce thefollowing relaI 45 Eq.11.6 we CO 45 m 2 with mass 45 ( ) ( ) = c / c = c / c R tions for45 theisotopic ratios: 44 45 44

I 44 CO 2 with mass 44 I 45 CO 2 with mass 45 = (c45 / c44 ) = (c45 / c44 ) 45 R m I 44 CO 2 with mass 44

and

( I 29 / I 28 ) sample

I 29 / I 28 ) reference

= 15 + 1 (11.9) ( 15 N / 14 N) reference ( 15 N / 14 N) sample 15 = 15 14 = +1 ( N/ N ) reference As reference or standard serves air N2 which shows very little variation: =
15

( N / N) sample

15

14

Theisotopic analysis of CO2 now proceeds in 3 or 4 steps, described in thenext sections. 11.2.3.1. Comparison with machine reference

I 46 CO 2 with mass 46 = (c46 / c44 ) = (c46 / c44 ) 46 R m I 44 CO 2 with mass 44 I 46 CO 2 with mass 46 (11.11) = (c46 / c44 ) = (c46 / c44 ) 46 R m I 44 CO 2 with mass 44

R(standard air N2)=0.0036765

(11.10)

Themass spectrometric precision obtained is about 0.02. However, thelaboratory samples handling to prepare theN2gas as required for theIRMS measurement results in much larger uncertainties, because thechemistry involved is less straightforward. For acheck of theoverall chemical and measurement procedures aset of reference materials is available. Thevalues are shown in Table11.1.

As with hydrogen, theionisation and transmission efficiencies of theisotopic molecules and ions are not 100%, so that thevalues of theproportionality factors c in Eq.11.6 can not be replaced by 1. This necessitates comparison of theion beam ratios with those of areference. Routinely laboratories use their own working reference gas (often referred to as theworking standard or machine standard, which finally has to be calibrated against theinternational stanTechniques de Mesure dard material). Eq.11.11 applies to thesample (s) and theworking reference gas (w), we eliminate theefficiency factors c themass <45> and mass m (I 45 /I 44 )s 45 R Techniques de Mesure pro= 45 S <46> measurements for and other (generally m (I /I ) R 45 44 r or multiplicative) w portional instrumental errors:
(I 45 /I 44 )s = (I 45 /I 44 )r
45 m RS 45 m Rw 46 m RS 46 m Rw

et TABLE 10.1. Reference materials 15 14 for N/ N analyses [108, 109].

Reference sample name IAEA-N1 IAEA-N2 IAEA-N3 USGS25 USGS26 USGS32 NSVEC Material (NH4)2SO4 (NH4)2SO4 KNO3 (NH4)2SO4 (NH4)2SO4 KNO3 N2gaz
15

() rel. toet air N2 +0.43 0.07 +20.41 0.12 +4.72 0.13

and (I 46 /I 44 )s = (I 46 /I 44 )r

(11.12)

11.2.3.2

m (I 46 /I 44 )s 46 RS = 46 m (IALIBRATION Rw 11.2.4. 46 /I 44 )r Calibration C

Thetrue isotopicisotopiques ratios of theworking reference, vrai valeur des rapports des rfrences de travail, 45Rwc et 46R 45 Rwc and 46Rwc, are known from arepeated comsuite une comparaison avec les standards internationaux, R1, (tels que 11.2.3.2 CALIBRATION +53.75 0.24 parison with rpte theinternational standards, R1, (such Les valeurs ces derniers peuvent tre calcules partir des vale as VPDB orde VSMOW). Thevalues of thelatter +180.00 VSMOW). La des rapports isotopiques de travail, 45Rwc et 46R 13 des 17 rfrences 18 18 vrai valeur be calculated from the R, R and R values R donnescan dans le Tableau 11.2. 2.78 0.04 suite une comparaison rpte avec les standards internationaux, R1, (tels que given in Table11.2. VSMOW). Les valeurs de ces derniers peuvent tre calcules partir des vale 18 R donnes dans le Tableau 11.2. 109
La 30.41 0.27

Pour 45 46 45RB. et 46 R

46 ecte 45 des standards sont obtenus par une correction R et R calibres la valeur correcte des standards sont obtenus par une correction Chapitre 11 INTRODUCTION c c 45 cc c c 45 RS R Rw R 45 c 45 m w R R multiplicatrice: 45 Rc = m S = w w 45 R ou 3,867 2,0878142 ou RSS = 45 VSMOW-CO m = m 45 m RSS 2 m m m R R R 45 46 S w R Rvaleur Rww sont obtenus par une correction 45 46 18 46 S w R et R calibres la correcte des standards R and c R calibrated to theproper values of (2) With these we calculate R from R 45 c c 45 c Rw 3,867 2,0878142 2,0879186 VSMOW-CO SMOW-CO 5 c 45 mR 2 2 Rw Rw 45 by c 45 m S multiplicatrice: RS = R thestandards are obtained amultiplicative (Eq.11.15) S = ou R = R 45 m S S m m 45 m Rw et (11.13) RS Rw Rw et correction: (11.13) 2,0879186 3,683 1,8939104 SMOW-CO2 SLAP-eau 17 (3) Now the R values can be calculated c c 45 c RS Rw R 46 c 45 c w 45 m 46 Rc = m rw R R 3,683 1,8939104 8 46 c c 46 m m 3,758 1,9719405 w 46 (Eq.11.16) SLAP-eau SLAP-CO S = 45 S 46 2 m m (11.13) RS = 46oR RS et (11.13) = R RS Rw R R m S S w 46 Rm w Rw 3,758 results in new 1,9719405 SLAP-CO2 (4) Inserting these in Eq.11.14 1 46 c ) Craig, 1957 Rw 46 m 13 and c 46 and better values for R (11.13) RS = 46 m RS et (11.13) Les rapports isotopiques, malgr tout tout toujours toujours2 appliqus la la molcule entire entire deCO CO sont ) Baertschi, 1976 1 2,sont R Les rapports isotopiques, malgr appliqus molcule de 2, w ) Craig, 1957 3 (5) This procedure is repeated until the13R, 17R 46 c maintenant calibrs. 2) Hageman et al., 1970; De Wit et al., 1980, assez bien confirm par Tse et al.( maintenant calibrs. R 46 c ) Baertschi, 1976 w 46 m Theisotopic ratios, however applying to R = molcule Rentire and 18R do no longer change. S 46 m oujours Sla detoujours CO2,still sont 45 entire 3 Les appliqus rapports isotopiques, malgr tout appliqus la molcule de CO sont R Les valeurs de R et 46R partir de: ) Hageman et al., 1 1970; De Wit et2,al., 1980, assez bien confirm par Tse et al.(19 al.(1 w molecule, are now calibrated. 1 sobtiennent theentire CO 2 Thevalues thus obtained for theisotope ratios of ORRECTIONS ISOTOPIQUES 11.2.3.3 C maintenant calibrs. CORRECTIONS ISOTOPIQUES 11.2.3.3 45 45 13 46 17 R= 213 R c and 18R c are R1 R et + R sobtiennent partir de: Les valeurs de 1R thesample automatically adS CO , sont S Les rapports isotopiques, malgr tout toujours appliqus lades molcule de 2contiennent Comme indiqu sur la Fig. Fig. 11.2, les faisceaux faisceaux ioniques des massesentire <45>et et <46>contiennent Comme indiqu sur la 11.2, les ioniques masses <45> <46> 11.2.4.1. Isotopic corrections 13 46 17 VSMOW 2 45 1318 17 13 17 justed on theVPDB or scales for C ES = 2 RR R= ++ 2 2R R R + R 11.2.3.3 C ORRECTIONS ISOTOPIQUES maintenant calibrs. diffrents ions isotopiques: 18 diffrents ions isotopiques: and O. The 17 values of thesample relative to As is shown in Fig.11.2, themass <45> and <46> 46 sceaux ioniques des masses <45> et <46> contiennent R = 218et R+ 213Rcontiennent R + 17R2 Comme indiqu sur la contain Fig. 11.2, les faisceaux ioniques <45> <46> ion beams different isotopic ions: des masses theinternational standard can now easily be writ12ISOTOPIQUES 16 16 13 16 16 16 12 17 17 16 16 11.2.3.3 CORRECTIONS 13 12 13 O 18 c O] c I44 =[ [12 C16 O16O] O] = [ C O16 O]+ +[[ C O] 44 = 45 diffrents ions isotopiques: ten as: I C O II = [ C O O] C O 45 RS RS 13 18 12 16 16 = = 1 1 et = [ C O O] I S/VPDB S/VPDB 13 18 44 Comme indiqu sur la Fig. 11.2, les faisceaux ioniques des masses <45> et <46> contiennent RVPDB 13 13 18 18RVPDB c c c c 13 16 12 16 16 16 12 17 16 R R 13 18 S S S S 13 16 16 13 16 16 + 16[12 C 12 17 16 13 17 16 I45 =ions [I44 Cisotopiques: O O] O O] 18 [ 16 12 17 17 S/VPDB = 1 and et 18 S/VPDB 1 [ 13C O] I+ [C C O [12C17 O13 O C O] 12 18 17 17 diffrents 45 S/VPDB S/VPDB = 18 45 = I46 =[ [O] C+ O16 O]O + [[13 C17O O16O] O] + [= [12 O O]O] + 13 O] 18 46 = C O O] + C C O O] I RVPDB R VPDB VPDB VPDB I46 = [12C18O16O] + [13C17O16O] + [12C17O17O] 12 16 16 13 16 16 12 17 16 18 c 16 17 17 16 17 17[ C O O] conduit aux rapports isotopiques suivants: = [12 C18 O16rapports O] + [13C = I44conduit RS O] + [12C17OCeci O] 45 Ceci isotopiques 18+ [ C O O] O O] O O] +suivants: [12CI O O] I 46 = [ C aux (11.18) = 1 S/VSMOW 18 This leads to theisotopic ratios: R 18 18VSMOW c c RS 18 18 S 13 16 16 16 16 12 17 16 16 12 17 17 S/VSMOW 1 uivants: 13 12 17 12 18 [16 13 17 16 S/VSMOW = 18 18 I 45 C O O] + [ C O O] Ceci conduit aux isotopiques suivants: 45 13 17 I [ C O O] + [ C O O] == [rapports C O O] + [ C O O] + [ C O O] I45 46R R 13 R + 217 R 45 = = (11.14) VSMOW VSMOW R= = = R+2 R (11.14) 12 16 16 16 16 12 18 I 44 [ C O O] I [ C O O] CORRECTION O POUR L EQUILIBRE EAUCO2 11.2.3.4 44 13rapports 16 16 isotopiques 12 17 16 O] Ceci conduit aux suivants: 13 17 [ C O O] + [ C O O] 18m 45 + 2 IR = R (11.14) 11.2.3.4 O L EQUILIBRE EAU CO2 on CORRECTION lexplique dans laPOUR Part. 10.2.1.1, on doit appliquer une correction s = = 13 R + 2 17Comme (11.14) R = 45 (11.14) R Rw Rm S 12 16 16 I 44 [ C O O] 18 12 18 16 13 17 16 12 17 17 I 46 [ [12 C18 O16 O] + + [13 C17 O16 O] + [12 C17 O O17du O] CO2 isotopique avec un chantillon deau. Cette corre 46 18 en quilibre 13 17 17 17 2 2 O O] 18 17 (11.15) 13 I 46 16 = 16 C O12 O] 17 [ 16 C O O] + [ C Comme on Part. 10.2.1.1, on doit 46 R [= = = 22lexplique R+ +2213 Rdans R++la R (11.15) = = R R R R measured values of 45R and R appliquer une correction su 12O] 16 16 16 I 4546 R C O O] + [ C O 45 13 17 12 16 I 44 C O O O] O] ce A stade de la procdure de calcul. La valeur corrige pour le CO 18 [[ C = I = (11.14)avec R= R + 2 applique RO du CO 44 12 16 16 en quilibre isotopique un chantillon deau. Cette correct correc 2 c I 44 [16 C O13 O] Rw Rc 12 18 17 2 16 12 17 17 (cf. Part. 4.3.2):R 1 S O] + [ 12 C 17 O 17 O] 18 13 17 17 I C+ O O] [ +C R O O](11.15) + [ C O O] 46 13 stade 17 17 la 2procdure de calcul. La valeur corrige pour le CO2 (11.15) 2[ R 2 45 R + R applique de (11.15) 46 16 16 13 13 12 17 16 18 16 R = 46= = = 2 18 R+ 2ce R+ R 46 16 O] En remplaant 45 R et et R dans dans C/12C, C, 17 O/16 O et 18 O/ O, R nous travaillons donc avec avec 3 1846 O] C/ I 44 remplaant En R R O/ O et O/ O, nous donc 3 [ 12 C O 18 18 travaillons 18 18 18 calibrated of 45 R and R (cf. Part. 4.3.2): Rc' = c/w 18R = (1values + w0 c/w ) Rc c/w Rc0 45 46 12 18 16 45 13 17 16 12 17 17 45 46 13 12 O 17 O] Ret et RR inconnues. Dun autre ct, nous pouvons seulement dterminer deux rapports, viz I 46 [ CDun O O] +[ C 46R O O] + [C/C . . 18 autre ct, nous pouvons seulement dterminer viz .. R R and into C, O/16O and In 16 translating 46 18 17 18 rapports, 17 182 18 13 Rdeux 18 (11.15) 18 = = inconnues. 2 R+2 R +c/w R Rw0 = 45 nous 46 travaillons 12 17 16 3 17 ou 18 =en 16 valeurs R ' = (1 + ) Rc 18c/w 18Rc0 12 13 16 donc 16 C, 17En O/16remplaant OR et O/ O, avec : c c/w 18 16 c 18 c I [ C O O] R et R dans C/ C, O/ O et O/ O, nous travaillons donc avec 3 O/ O, we are thus dealing with 3 unknowns. 17 18 44 R R R La relation thorique thorique entre entre labondance labondance en en O O et et O O de de loxygne, loxygne, est la latroisime troisime donne 1 S 2 La relation est donne 46 18 18 18 45 18 46 18 On theother hand we can only 2 raR et determine R. dterminer ons seulement dterminer deux rapports, viz . 45 ou en valeurs : ' = (1 + ) R et R . inconnues. Dun autre ct, nous pouvons seulement deux rapports, viz . c c/w c c/w c0 ncessaire (Part. 3.6): 46 13 12 17 16 45 463.6): ncessaire (Part. calibrated values of 13R or 18R 18 tios,45 viz. and R. Thethird given required is nous travaillons 17 remplaant R et R R dans C/ C, donne O/ O/16O, donc avec 18 3 En B 17 O et 18 e en La Orelation et 18O de loxygne, est la troisime 18 18 18 18 17 thorique entre relation labondance en the Ode et de 18 loxygne, est donne Techniques Mesure n c' R = (1la + troisime c/w )R n c c/w c0 thetheoretical between OO and O R2 45 46 1 S 186 R et R . inconnues. Dun autre ct, nous pouvons seulement dterminer deux rapports, viz . 186 ORMALISATION 11.2.3.5 N abundance ncessaire (Part. 3.6): in natural oxygen (Sect.3.6): normalised values of 13R or 18R La relation thorique entre labondance en 17O et 18O de inter loxygne, est la troisime donne 17 18 Les comparaisons entre laboratoires ont indiqu des diffrences consid 11.2.3.5 NORMALISATION RS RS 186 (11.16) isotopiques effectues (11.16) = 18 17 ncessaire (Part. 3.6): mesures sur des matriels identiques. of On a aussi montr Fig. 11.3. chematic representation procedures Rr Rr Les inter comparaisons entre laboratoires ont of indiqu des diffrences considr consid calibration ( A) utilisant and normalisation (B) of isotopic pouvaient tre rduits en deux standards au lieu dun. Les valeurs mesures isotopiques effectues sur des matriels identiques. On a aussi montr q 186 analyses. where s and r refer to asample and thereference, peuvent dans certains cas tre corriges partir du fait que le rapport (pour R ou s et r serespectively. rapportent, respectivement, lchantillon et la rfrence. Le plus simple est standards au lieu dun. Les valeurs ) pouvaient tre rduits en utilisant deux A. Themeasured values of 45Rmstandard and 46Rm are calibrat) mesurs entrecas R1 tre et le deuxime de la vrai (tablie (pour 2 scarte dutiliser une procdure itrative pour rsoudre les quations ci-dessus pour lchantillon et le partir duR peuvent dans certains corriges fait que (R le ) rapport (pour R) o ed (i.e. adjusted to the international standards 1 It is theeasiest to use an iterative procedure 45 to 46 45 c 46 c standard, en partant des valeurs mesures et corriges de R et R : ) mesurs entre R1 et le deuxime standard R2and scarte de la vrai (tablie) (pour such as VPDB and VSMOW) to give R R;R w solve theabove equations for sample and stanand R are corrected proportionally. 17 13 45 188 dard, starting from themeasured (1) On utilise lapproximation R = 0 et ainsi and R = corrected R (Eq. 11.14) S B. For normalisation the13R or 18R scale is stretched 45 46 values for R 18 and R: 46 188 in order to reach the established value for a second (2) Avec cela on calcule R partir de R (Eq. 11.15) 17 R =0 and (1) We apply theapproximations standard (R2n). Thecorrections to theR2 and RS values 17 13 peuvent 45 (3) Les valeurs de R alors tre calcules (Eq. 11.16) thus R= R (Eq.11.14) is again proportional.

nouveau proportionnelles. normaliser, lchelle 13R ou 18R est tendue de manire atteindre la valeur calibres la la valeur valeur correcte correcte des des standards standards sont sont obtenus obtenus par par une une correction correction R et R calibres connue dun deuxime standard (R2n). Les corrections pour les valeurs de R2 et RS sont de multiplicatrice: Chapitre 11 multiplicatrice: nouveau proportionnelles.

(4) En introduisant cela dans lEq. 11.14 on obtient de nouvelles et de meilleures valeurs de 13 R 110 (5) Cette procdure est reproduite jusqu ce que 13R, 17R et 18R ne changent plus. Les valeurs de
13

RSc et

18

RSc ainsi obtenues pour les rapports isotopiques sont

measuring techniques

11.2.4.2.

O correction for waterCO2 equilibration

18

11.2.4.3. Normalisation Laboratory intercomparisons have shown aconsiderable spread in isotopic results from different laboratories on thesame materials. It also has been shown that this spread can be reduced by applying two standards instead of one. TheR and values may in certain circumstances be corrected for thefact that theratio (for R) or distance (for ) as measured between R1 and thesecond standard R2 deviates from thetrue (established) value. In this procedure of normalisation theR or scale is so-to-speak stretched proportionally to reach theestablished ratio or distance for R and . This procedure of inter- or extrapolation is represented by Fig.11.3B and is mathematically written as:

As was explained in Sect.10.2.1.1, we have to apply acorrection for the18O content of theCO2 brought in isotopic equilibrium with awater sample. This correction has to be applied at this stage of thecalculation procedure. Thecorrected value for theequilibrated CO2 is (cf. Sect.4.3.2):
18

Rc = 18c/w 18Rw0 = (1 + 18c/w ) 18Rc 18c/w 18Rc0 (11.19)

or as values:
18

c = (1 + 18c/w ) 18c 18c/w 18c0

(11.20)

TABLE 10.2. Absolute isotope ratios needed for thecalculation procedure of calibrated and normalised isotope ratios.
Reference material PDB-CO2 SMOW-CO2 VPDB-calcite VPDB-CO2 NBS19-calcite NBS19-CO2 VSMOW-water VSMOW-CO2 SMOW-CO2 SLAP-water SLAP-CO2 [40] [60] c [70, 71] reasonably well confirmed by [72].
a b 13

R 102

17

R 104

18

R 103

R 106

1.12372 a 1.12372000 1.12372000 1.12591025 1.12591025

3.800 3.788666 3.808033 3.784496 3.803842 3.790 3.867 3.683 3.758

2.0790 2.0785 2.0671607 2.0883491 2.0626129 2.0837547 2.005b 2.0878142 2.0879186 1.8939104 1.9719405 89.07 c 155.76 c

Note: The13R values are based on theoriginal value of 13R for PDB by [30] as quoted by [40]. The18R value are based on theabsolute measurement of 18R of VSMOW-water by [60] and known values for thefractionations as given in Fig.6.10. 17R values are based on theabsolute measurement by [110] and thesquare roots of thevarious 18O fractionations. Thevalues in theshaded box are now obsolete. 2R values are theaverages of thereported data. Thevalues for 45R1 and 46R1 are obtained from: 45 R=13R + 217R (11.17a) 46 R=218R + 213R17R + 17R2 (11.17b)

111

INTRODUCTION

TABLE 10.3. values of isotopic standards, and reference and intercalibration samples measured on CO2 prepared by (i) combustion of organic compounds, (ii) equilibration of CO2 with water at 25C, or (iii) decomposition of carbonates with orthophosphoric acid (95%).
Reference NBS1 NBS1A NBS16 NBS17 NBS18 NBS19 NBS20 NBS21 NBS22 VSMOW GISP SLAP IAEA-CO1 IAEA-CO8 IAEA-CO9 LSVEC IAEA-C6 IAEA-CH7 USGS24 GS19 GS20 Material water water CO2 CO2 carbonatite marble limestone graphite oil water water water marble calcite BaCO3 Li2CO3 sucrose poly-ethylene graphite CO2 CO2
13

()

18

()

() 0.00

Fourni par exhausted exhausted exhausted exhausted NIST/ IAEA NIST/ IAEA not distributed exhausted NIST NIST/IAEA NIST/IAEA NIST/IAEA NIST/IAEA NIST/IAEA NIST/IAEA NIST/IAEA IAEA IAEA NIST CIO CIO

7.94 24.33 35.98 18.61 23.00 2.20 4.14 0.00 24.79 55.50 2.44 22.67 15.28 26.46 0.19 0.99

41.60 4.51 5.03 +1.95 1.06 28.16 29.74 + 2.48 5.75 47.12 46.48 10.43 31.83 15.99 7.50 8.62

189.7 428.0 100.3

Note: 13 values are relative to PDB or VPDB, 18 of CO2 to VPDB-CO2, 18 and 2 refer to SMOW or VSMOW. Certain reference samples are now obsolete and only quoted for historical interest [108]. NISTNational Institute of Standards and Technology, Atmospheric Chemistry Group, B364, Building 222, Gaithersburg, MD 20899, United States of America IAEAInternational Atomic Energy Agency, Analytical Quality Control Services, Agencys Laboratory, Seibersdorf, P.O.Box 100, A1400 Vienna, Austria, fax +431206028222 CIOCentre for Isotope Research, Nijenborgh 4, 9747 AG Groningen, theNetherlands, tel. +31503634760, fax +31503634738

112

. Cette dinterou extrapolation atteindre le rapport la tablis R et Techniques de Mesure Dans cette procdure dedistance normalisation, lchelle de R ou procdure calculer est,techniques pour ainsi dire, tendue pour est reprsente sur ou la figure Fig. 11.3B etpour scrit mathmatiquement ainsi: measuring Pour les rapports isotopiques partir de des rapports des faisceaux (e Techniques Mesure Techniques de Mesure est reprsente sur la figure Fig. 11.3B et scrit mathmatiquement ainsi: atteindre le rapport ou la distance tablis pour R et . Cette procdure dinterou extrapolation utilise la mme dmarche que prcdemment: n n RS R est reprsente sur la Pour calculer ainsi: les rapports isotopiques partir de des rapports des faisceaux (ex 2 figure Fig. 11.3B et scrit mathmatiquement n = calculer n (11.21) Techniques Mesure Pour calculer les rapports isotopiques O] partir des rapports des faisceaux (e 18 16 17 Pour les rapports isotopiques partir des rapports des faisceaux (exposant m) on c c R R I [ O + [ O ] S 2 m 34 R R 34 2 utilise la mme dmarche que prcdemment: S= 2 (11.21) (11.21) R = = ( c / c ) = (c34 / c32 )(2 18 R + 17 R 2 ) c cla mme dmarche que prcdemment: 34 prcdemment: 32 utilise la mme dmarche que 16 Rutilise R n n I [ O ] S 2 32 2 R R S = 2c (11.21) I 34 Pour calculer isotopiques partir des (e + [ 17 [ 18 O16 O] O 18 16 c 18 16 17 34 les m rapports 18 faisceaux 2 ]] rapports des I isotopique [ O] + [ 17 O I 34 et standard O et O] + RS standard Rto = (18 c34 / c32 R + 1717 R2 ) ,[ laO composition finale Par rapport Related au international crit en[ valeurs 2 and written 2 = (c34 / c32 )( 2 18 m 34 17 ) 2 O 16 2 ] 34 R m = 34 2 theinternational = I32 = c34 c32R = (c34 / c32 )(2 R + R ) /prcdemment: ) ) [ 16 R = = ) =R (c )( 2 (que R+ O2 ] utilise la composition mme dmarche 34 / c 34 / c32 16 , la Par rapport au international et(c crit en isotopique finale as standard values, the finalI 32 calibrated as valeurs well [ as I32 [ O Onor calibre et normalise est: 32 2] 2] 17 16 malised isotopic composition of thesample calibre et normalise est:international I 33 [ O16 O] O] + [ 17 O ] 33 17 m [ 18 O et is: Par rapport au standard et crit en valeurs , la composition finale 34 R m = I 34 isotopique 2 c32 )( 2 R ) = c c = ( / ) (c33 / 33 32 et 16 R = = c c = (c34 / c32 )(2 18 R + 17 R 2 ) ( / ) et (11.24) and n c m 34 32 n n 16 I [ O ] 32 RS R R RS R2 I 32 [2 O 2 ] calibre et normalise est: n m n = (1 + ) = R n2c R cw R m = Rn (1+ 17 (1 + S/w ) (11.22) I 33 [ 17 O16 O] w/ 1 ) 17 16 m c 33 m 16 RR nS/ 1 m S w S 2 2 I [ O O]=(spcifiques I 33Rw = R2 (1 + [ R m 17 = 33 = (c33 / c (c33 / c32 )(2 17 R ) O] 17 33 R m 1 = (1 + 2 R1 O) (Aprs + = (11.22) )= 1 ) / c 33 )( 32 ) 16 correction des erreurs instrumentales chaque appareil et d S/w R = = ( c / c ) = (c33 / c32 )(2 R) c = m c c ) w/ 1 et S/ 1 R = ( c / ( c 2 R ) I 32 33 32 [ 16 O2 ] 33 33 32 16 R R R n n R1 c Rwm n 32 1 2 2 I [ O ] I [ O ] (11.22 RS R2 Rw32RS R2 32 2 2 n m du moment de la (11.22) mesure), les valeurs de correspondantes sont: = (1+ S/ 1 ) = c = c (1+ w/ 1 )probablement (1 + S/w ) 2 m La procdure applique aux analyses de 18 et H de leau, dans I 33 Rde R1souvent [ 17 O16 O] (spcifiques 17 R2 est Rw R Aprs correction des erreurs instrumentales chaque appareil et d 33 mO Thenormalisation procedure is ap1 normalisation 2 often being 18 2 = (c Aprs correction des erreurs instrumentales (spcifiques appareil et d R = c = R) / ) (c33 / c32 )(2 chaque Aprs correction des erreurs instrumentales (spcifiques chaque appareil et16dpendant aussi 32 dans La de normalisation est souvent applique auxloigns analyses de lchelle O34 et HVSMOW de33leau, 2 m la procdure mesure o dans cethe cas 18 deux standards suffisamment sur sont O and H analyses of water, as plied to I [ O ] (11.24) 34 18 17 2 probablement du moment de la mesure), les valeurs de correspondantes sont: 32 2 R Rs les 2 Rs + de Rs correspondantes samplede la mesure), 34 du sont: probablement moment valeurs probablement du moment desuffisamment la mesure), les valeurs de correspondantes sont: 18apart 16 2 1 la mesure o dans ce cas deux standards loigns sur lchelle sont 18 2 VSMOW = 1 = 1 = 1 here two standards relatively wide on disponibles. Les valeurs de R et R sont les valeurs O/ O et H/ H du VSMOW et du SLAP m 34 34 18 17 2 La procdure de normalisation 1 est2 souvent applique aux analyses de O et H de leau, dans After correction for instrumental errors (specific R R 2 R + R 18 Aprs 2 1 reference instrumentales r r chaque appareil et d correction des erreurs (spcifiques and theVSMOW scale are available. The R1 disponibles. Les valeurs de deux R sont les valeurs O/16 O et H/prcdent. H du VSMOW et du 34 SLAP 34 m 1 et R2 18 17 2 (Standard Antarctic Precipitation) indiqu la mesure Light o dans ce cas suffisamment loigns sur lchelle VSMOW sont m normalisation 34 RLa 2 R + R 34 16 m 34R 18 17 2instru18 standards 2 34 1sur le tableau sample 18 17 2 34 and probably time-dependent for each s s s RLa are 34 the O/Rsample O or indiqu the H/R H values R2 values Rs 1 les R + de R 2 of Rs2 +prcdent. R 1 = 2 correspondantes 1 probablement du moment de la=mesure), valeurs sont: sample 34 (Standard Antarctic Precipitation) sur tableau normalisation s 18 le s= 16 1 34 m 34 18 s 17 2 s 1 = 1 = 1 = = 1 = 1 = 1 peut aussiLight scrire entirement en termes de valeurs et est alors approche par disponibles. Les valeurs de R et R sont les valeurs O/ O et H/ H du VSMOW et du SLAP R R 2 R + R 1 34 2(Standard m 34 34 r values 18are: 17 r 2 ment), thecorresponding m 34 18 17 2 VSMOW and SLAP Light Antarctic reference et Rpar Rr 2 R + Rr Rreferencede valeurs Rr et est2alors R + Rr reference peut aussi scrire entirement termes Precipitation) as en given in indiqu theabove (Standard Light Antarctic Precipitation) sur le table. tableauapproche prcdent. La normalisation 34 m 34 Rsample Rs 2 18 Rs + 17 Rs2 n m 34 Normalisation can also be de written entirely in approche m 33 par S/VSMOW = 34 1 = 1 = 1 33 17 17 peut aussi scrire entirement en termes valeurs et est alors et S/VSMOW 34 R 18R 17 2 R Rm n = mmand is then approximated (11.23) sample 33 et by s R Rsr 1 = 2 2(11.25) Rs + R et terms of values n reference 1 = r = 1 = 1 S/VSMOW S/VSMOW SLAP/VSMOW = SLAP/VSMOW 33 m 33 17 Rreference (11.23) Rr 2 17 Rr Rr n m SLAP/VSMOW and 33 R m n 33 17 SLAP/VSMOW S/VSMOW m 33 m m 2 17 Rs Rs 33Rs 17 17 sample 33 17 33 R Rsample = 33 mS/VSMOW (11.23) R 2 R Rs 1 (11.23) Rs et 2 17 Rs 33 1 = 1 = sample 1 = 33 = R s s n s 33 m 33 17 17 = 1 = 1 = 1 = 1 = 33 isotopiques 1 =et33 1 = 17 et 1 = 17 33 R reference 1 des18 Tableau 11.3.Valeurs des standards des rfrences, intercalibration chantillons SLAP/VSMOW 17 2 17Rrde rfrence Rr m 33R 17 SLAP/VSMOW m r Comme les valeurs R et R des chantillons standard sont c r r R R 2 R Rr ou R Rr rfrences, 2 Ret Rr reference r r reference r intercalibration Tableau 11.3.mesurs Valeurs sur des standards isotopiques et des des chantillons le CO2 prpar par (i) combustion de composs organiques, quilibration 17 m (ii)18 17 17 18 33 n 33 17 (11.25) Rs et Rs, et donc calculer facilement using the levalues: R Rs les valeurs 2 Rs de et R . mesurs CO par (i)ou combustion de composs organiques, (ii) quilibration 33 2 prpar 17 sample 18 du CO2sur avec leau a isotopiques 25C, (iii) de carbonates avec = 1 = lacide 1 = 17 de 1 = 17 s ou 1standard sont co Tableau 11.3. Valeurs des standards et desdcomposition rfrences, et intercalibration des chantillons Comme les valeurs R des chantillons rfrence 18 r 17 18 m r et 33 17R 33 17 avec 18R Comme les valeurs Rr standard et R chantillons de rfrence ou standard sont c 13 du CO2 avec leau a 25C, ou (iii) dcomposition de par carbonates lacide R 2 R R Comme les valeurs RLes Rr des chantillons de rfrence ou sont connus, on peut r des R and values for thereference Because the r et valeurs reference r r r r r orthophosphorique (95%). de sont exprimes rapport au PDB ou au 2 17 18 quilibration 17 18 mesurs sur le (i) combustion de composs 17 organiques, (ii) SLAP/VSMOW =CO 428.0 or 18 2 prpar par R , et donc les valeurs de et . 13 calculer facilement 17Rs et 18 17 18 s 17 18 17 18 18 2 par orthophosphorique (95%). Les de les sont exprimes rapport PDB ou ou au R etau R et are donc les valeurs de 18 . RADIOAC calculer facilement samples or known, R Rset , and R et valeurs Rou , etVPDB-CO donc valeurs de etrfrent . sstandards calculer facilement 11.3 RADIOMETRIE LES ISOTOPES s, POUR s sau s and VPDB, lesavec du CO rapport se auavec SMOW 2 par 2, les et de du CO leau a 25C, (iii) dcomposition carbonates lacide 2 2 2 18 2 17 18 17 18 RSLAP = 0.5720 RSMOW VPDB, les du CO rapport aude VPDB-CO les 18 et se rfrent SMOW ou thus the rand can be easily calculated. 13 Comme 2 par 2, sont les valeurs R et au des chantillons de rfrence ou standard sont c r values au VSMOW. Certains chantillons rfrence aujourdhui obsoltes et ne ou sont orthophosphorique (95%). Les valeurs de Pour sont exprimes parradioactivit, rapport auR PDB au dinstruments mesurer la nombre sont disponibles, chac 17 18 17 18 11.3 RADIOMETRIE POUR LES ISOTOPES au VSMOW. chantillons de rfrence sont aujourdhui obsoltes et ne sont les 18 Certains 18 2 prsents que pour leur intrt historique (donnes de lAIEA, 1995). R et R , et donc valeurs de et .RADIOACT calculer facilement s s and 11.3 RADIOMETRIE POUR LES ISOTOPES RADIOAC VPDB, les du CO par rapport au VPDB-CO , les et se rfrent au SMOW ou 11.3 RADIOMETRIE POUR LES ISOTOPES RADIOACTIFS 2 2 avantages spcifiques prsents que pour leur intrt historique (donnes de lAIEA, 1995). et leurs dsavantages. Les principaux instruments do au VSMOW. Certains chantillons de rfrence aujourdhui obsoltes et ne for sont 11.3. Radiometry radioactive Poursont mesurer la radioactivit, dinstruments sont disponibles, sont (i) les compteurs a nombre gaz et (ii) les spectromtres scintillationchacu liqui 18 Pour mesurer la radioactivit, nombre discuter Pour mesurer la radioactivit, nombre dinstruments chac dinstruments sont disponibles, chacun avec leurs sonta disponibles, SLAP/VSMOW = 55.50 or prsents que pour leur intrt historique (donnes de lAIEA, 1995). isotopes avantages spcifiques et leurs dsavantages. Les principaux instruments don 11.3 RADIOMETRIE POUR LES ISOTOPES RADIOACT 13 18 2 avantages spcifiques et leurs dsavantages. Les principaux instruments do et leurs dsavantages. Les deux principaux instruments dont nous allons peut tre mesur comm Avec ces techniques, lchantillon radioactif Fourni par Rfrence Matriel 18 avantages spcifiques 18 RSLAP = 0.9445 RSMOW discuter sont (i) les compteurs a gaz et (ii) les spectromtres a scintillation liquid 13 18 2 For measuring radioactivity anumber of instruFourni par Rfrence Matriel discuter sont les compteurs a gaz et (ii) les spectromtres a disponibles, scintillation liqui spectromtres discuter sont (i) les compteurs a gaz et (ii) les a scintillation liquide. Pour mesurer la radioactivit, nombre dinstruments sont chac interne il(i) est mlang ou il est une partie intrinsque du milieu de compta () () , i.e. ments () are available, each with their specific ad Avec ces deux techniques, lchantillon radioactif peut tre mesur comme Table11.3 contains the values of theisotopic 13 18 2 avantages leurs dsavantages. Les principaux instruments do fonctionnement de linstrument. Cela comporte les avantages suivants: () () Fourni par Rfrence Matriel Avec deux lchantillon radioactif peut tre mesur comm ces spcifiques techniques, Avec ces deux techniques,() lchantillon radioactif peut treetmesur comme une source vantages and ou disadvantages. Themain instrupuis standardseau and theavailable reference intercom 7,94 , i.e. NBS1 interne il(i) est mlang il est une partie intrinsque du a milieu de comptag discuter sont les compteurs a gaz et (ii) les spectromtres scintillation liqui interne , i.e. il est ou ilcomptage, est une partie intrinsque milieu de besoin compta interne ,eau i.e. il est mlang ou il est une partie intrinsque du milieu de charge du anddu eau puis 7,94 mlang NBS1 1) Les particules formes par la dcroissance radioactive nont pas () () () parison samples. ments will discuss are (i) gas counters (ii) puis 24,33 NBS1A fonctionnement de we linstrument. Cela comporte les avantages suivants: fonctionnement de linstrument. Cela comporte les intressant avantages suivants: fonctionnement de linstrument. les avantages suivants: Avec ces deux techniques, lchantillon radioactif peut tre mesur comm eau puis 24,33 Cela comporte NBS1A parois de linstrument; cest particulirement pour la dtection liquid spectrometers. CO puis 41,60 35,98 NBS16 eau2 puis 7,94 scintillation NBS1 3 14 1) Les particules formes par la dcroissance radioactive nont pas besoin d interne ,de i.e. il est mlang ou ilH est une partie ducas, milieu de compta CO puis 18 16 41,60 35,98 NBS16 2 laWith dsintgration du et du car intrinsque dans les deux lnergie es 1) Les particules formes par latheradioactive dcroissance radioactive nont pas besoin O/ O and 11.2.5. Measurement of 1) Les particules formes par la dcroissance radioactive nont pas besoin deC pntrer les eau puis CO puis 24,33 both NBS1A 4,51 18,61 NBS17 2 techniques sample is 17 16 parois de linstrument; cest particulirement intressant la dtection fonctionnement de linstrument. Cela comporte les avantages pour suivants: CO puis O/ O2 4,51 particulirement 18,61 NBS17 2 dein parois de linstrument; cest particulirement pour la dtection parois linstrument; cest intressant pour la dtection des particules CO puis carbonatite NIST/ AIEA 41,60 35,98 NBS16 measured as an internal source , i.e. intressant it is mixed 5,03 23,00 NBS18 2 2) Lefficacit de comptage est langle de dtection tant de 3 presque 14 de 100%, du 3H AIEA et du 14 C car dans les deux cas, lnergie est de la dsintgration 3 CO , two NIST/ 23,00 NBS18 This analysis includes, as with meade lales dsintgration du par H et C dans les deux cas, lnergie es dans 1) Les particules cas, formes la dcroissance radioactive nont pas besoin with, is an intrinsic part ofcar thecounting mede la H et 2du 14 C car deux lnergie du est trs faible. carbonatite CO puis marbre +1,95 NIST/ AIEA 5,03 4,51 18,61 or NBS17 2,20 NBS19 2 dsintgration du surements, i.e. of theion beam ratios for2) masses marbre +1,95 NIST/ AIEA 2,20 NBS19 dium, for theoperation ofintressant theinstruLefficacit deresponsible comptage est presque de 100%, langle de dtection tant de parois de linstrument; cest particulirement pour la dtection carbonatite NIST/ AIEA calcaire non fourni 1,06 5,03 23,00 NBS18 de 4,14 NBS202) Lefficacit 11.3.1 COMPTEURS A GAZ 2) Lefficacit dede comptage est presque de de comptage est presque 100%, langle dtection tant de 4 . 100%, langle de dtection tant de <34>/<32> and <33./<32>, while thenumber of 3 fourni 14 advantages: calcaire non 1,06 4,14 ment. This has thefollowing NBS20 du H et du C car dans les deux cas, lnergie es de la dsintgration marbre +1,95 NIST/ AIEA 2,20 NBS19 and 17O/16O. Thus, unknowns is also two: 18O/16O 189 Bien que lutilisation des divers compteurs a gaz soit diffrente, la constructi 11.3.1 COMPTEURS A GAZ has to be made contrary to CO2, no assumption calcaire non fourni (1) The particles from theradioactive decay do 1,06 4,14 NBS20 189 11.3.1 COMPTEURS A GAZ 2) Lefficacit de comptage est presque de 100%, 11.3.1 COMPTEURS A GAZ identique. Le principe est indiqu sur la Fig. 11.4. langle de dtection tant de for therelation between the18O and 17O fractionnot need to penetrate thewall of theinstruBien que lutilisation des divers compteurs a gaz soit diffrente, la constructio 189 de Bienaque des divers compteurs a gaz soit diffrente, la constructi ations. More than that, from these compteurs measurements Bien que lutilisation des divers gaz lutilisation soit diffrente, la construction base est ment; this is especially relevant to detecting identique. Le principe est indiqu sur la Fig. 11.4. 11.3.1 COMPTEURS A GAZ therelation thetwo fractionations can be Le principe identique. est indiqu Fig. 3 14 11.4. identique. between Le principe est indiqu sur la Fig. 11.4. - particles from sur H la and C decay as in both derived. Bien que lutilisation divers compteurs a gaz soit diffrente, la constructi casesdes the energy is very small 191 To calculate theisotope ratios from themeasured identique. Le principe est indiqu sur la Fig. 11.4. (2) The counting efficiency is nearly 100%, (superscript m) ion beam ratios asimilar procethedetection angle is 4p. dure is chosen as previously:
113

Techniques dede Mesure Dans cette procdure de normalisation, lchelle R ou est, pour ainsi dire, tendue pour Techniques de Mesure Dans cette procdure de normalisation, lchelle de R ou est, pour dinterainsi dire, tendue pour atteindre le rapport ou la distance tablis pour R et . Cette procdure ou extrapolation

INTRODUCTION

11.3.1. Gas counters Although theoperation of thevarious gas counter types is different, thebasic construction is thesame. Theprinciple is shown in Fig.11.4. Basically there are 3 different types of gas counters, depending on themagnitude of thehighvoltage applied between thewire and thecounter wall: (1) theionisation chamber, (2) theproportional counter, (3) theGeiger-Mller counter. The counters are filled with a counter gas, required to have suitable ionisation characteristics. 11.3.1.1. Ionisation chamber Theincoming radiation, that is, aparticle originating from adecay reaction inside or outside thecounter tube, looses its energy by collisions with gas molecules in thecounter. These events cause themolecules to become ionised. In theelectric field inside thetube, theheavy positive ions slowly move towards thewall and become neutral by picking up electrons. Thesmall, negative primary electrons set free by thecollision become accelerated towards thepositive central wire. After being collected by thewire, these electrons are observed as asmall electric current or an electric pulse in thewire. In theelectronic circuitry, attached to thecounter, this pulse is registered and thepulse size measured. This is representative for thenumber of primary electrons and thus of theenergy of theincoming particle. In this way information is obtained about theradioactive decay event. 11.3.1.2. Proportional counter Theprimary electrons are accelerated in theelectric field between the wire and counter wall. If the voltage on the counter wire is sufficiently high, theprimary electrons, accelerated towards thewire, obtain enough velocity and energy to ionise other gas molecules and so create more free electrons. Thesame is true for these new electrons and so on and so forth. In this way an avalanche of electrons is created moving towards and collected by thewire (Fig.11.5). This phenomenon is called gas multiplication. Theresulting electric pulse is proportional to this gas multiplication (and thus depending on thehigh 114 voltage) and is still proportional to thenumber of primary electrons and thus to theoriginal energy of theincoming particle (Proportional Gas Counter, PGC). 11.3.1.3. Geiger Mller counter During operation as aproportional counter thesecondary electron avalanche is very local. At very high voltage, however, thesecondary ionisation process extends over theentire length of thecounter tube. Thepulse size is maximal and no longer depends on theenergy of theincoming particle or thewire voltage: in theGM counter theexistence of theparticle is registered, but it can not be recognised, as in thecase of theproportional counter. This is, however, essential in order to be able to distinguish theparticle (for instance, a- particle from 3H or 14C) from strange particles. Our conclusion, therefore, has to be that theonly suitable gas counter for our purpose is theone which operates as aproportional counter. This equipment was the first established for measuring theradioactivities of 3H and 14C. These atoms have to be brought in agaseous form suitable for operation in acounter as sample as well as counting gas. This is essential because the radiation can not penetrate thecounter wall, the energies being extremely low (Fig. 8.2). Later another technique came into use, i.e. theliquid scintillation spectrometer.
central wire at high voltage
10 to 50 cm

counter wall at ground potential counting gas

Fig. 11.4. Cross section of a gas-filled counter tube for detection of radioactive radiation. The ionisation phenomena in thecounter are shown in thecross-section of Fig.11.5.

measuring techniques

counter wall at earth potential incoming primar y electrons

particle

secondary electrons gas multiplication ~10 5 central wire at high voltage

Fig. 11.5. Lateral cross section through a gas counter. An incoming particle looses its energy through primary ionisation. At low voltage only these electrons reach thewire resulting in asmall electric pulse (ionisation chamber). If thevoltage is sufficiently high, thenumber of primary electrons can be multiplied by afactor of 105 (PGC). At very high voltage thesecondary ionisation is maximal and theelectron avalanche occupies the entire length of the counter: the pulse height is no longer depending on theincoming particle energy or thevoltage (GM counter).

Thebackground of thecounter, i.e. thecounting rate (number of counts per sec.) of thecounter without aradioactive source, in our case CO2 and C2H2 or H2 without 14C or 3H, respectively. This background has to be subtracted from theoverall counting rate. In order to minimise thebackground which would otherwise be orders of magnitude larger than theactual (net) counting rate we are interested in- thecounter is made of low-activity materials and shielded against radiation of thesurroundings (see Fig.11.6). Most counters are made of copper or quartz with sizes ranging between 0.5 and afew litres, although also mini-counters exist. An international compilation was made by [44]. In principle, thedata handling of radiometric equipment is simple. After acertain measuring time tm anumber of Nt disintegrations in thecounter have been observed. Thestatistical uncertainty or standard deviation of this number is N . This gross counting rate of Nt/tm (counts per sec) has to be diminished by thebackground B (counts /s) to give thenet counting rate A (see Sect.13.3.3): A(t) = Nt/tm B (11.26)

11.3.1.4. Counter operation At both ends of theproportional gas counter (PGC) thegeometry is distorted and thus theelectric field. Thedetection of particles from radioactive decay is, therefore, less efficient. Theconsequence is that theoverall counter efficiency is not exactly known: routinely an absolute measurement is not feasible. Thesolution to this problem is to perform arelative measurement: thesample is to be measured under exactly thesame conditions as areference sample, or, finally, as an international standard (Sect. 8.1.2), or thedependence of thedetected radioactivity of asample on thevarious parameters has to be exactly known. Without going into detail, we mention theessential parameters [82].

This result has to be standardised, i.e. has to be corrected to astandard amount of sample gas in thecounter, simply by applying theLaw of Gay-Lussac, in other words by multiplying by thepressure and temperature ratios:

A(t ) =

T p0 273.15 105 A' (t ) = (11.27) T0 p t + 273.15 p (in Pa )

Theamount of gas in thecounter; since sample and reference are being measured in thesame Theinternationally established standard (Oxalic counter, thecounter volume (V) is not relevant, Le standardAcid) tabli has internationalement oxalique) doit tre mesur dans to be measured (lacide under exactly thesame so that measuring thepressure (p) and temperaThen theactivity ratio can be calcuexactement conditions. identiques. Alors le rapport dactivit peut tre calcul comme le ture (T) is sufficient: the amount of gas= V.p/T lated as theratio between these two activities deux activits (Eq. 8.4). with T=t + 273.15 K. (Eq.8.4). La condviation standard de lactivit mesure est (le standard dans lexp Thepurity of thecounting gas; if thegas Thestandard deviation in themeasured activity is tains electronegative impurities, i.e. gas molngligeable): (standard in B is negligibly small): ecules with astrong attraction to electrons, part of theprimary and secondary electrons are lost, 1 A+ B N = A N = decreasing thepulse size and thecounting rate (11.28) t tm m [111]. 115 11.3.2 SPECTROMETRE A SCINTILLATION LIQUIDE
11.3.2.1 PRINCIPE PHYSIQUE

Now we have obtained thestandardised absolute (Sect.8.1.2). activity: 3A for 3H, 14A for 14C Chapitre 11

INTRODUCTION

iron para n + boric acid lead old lead

14 C or 3H counters

Geiger Mller counters

Fig. 11.6. Cross section of atypical counter set-up with shielding against radiation from thesurroundings, including cosmic radiation. TheGM counters operate in anti-coincidence with theproportional counters in themiddle. Thelow-mass hydrogen atoms in paraffin are very efficient in reducing the(penetrating) energy (speed) of high-energy neutrons. Boron has ahigh absorbing capacity for low-energy neutrons. Thehigh-mass lead absorbs radiation. Old lead has lost theradioactive lead isotope 210Pb (RaD), due to its short half-life (22a).

11.3.2. Liquid scintillation spectrometer 11.3.2.1. Physical principle This method is based on theprinciple that certain materials emit light after their molecules have been excited by collisions with high-energy particles. This process, called luminescence, takes place in aproper solid or liquid. Our interest is focussed on theuse of liquids, because there are methods to transfer carbon (including 14C) to benzene which -with some precautions- is suitable as ascintillator, whereas water (with 3H) can be mixed with ascintillating liquid, acommercially available cocktail of various constituents. Therequirement of this mixture is that it mixes well with water, transfers theprimary electron energies into fluorescent energy, and finally into low-energy fluorescent light within thesecondary-emission range of thephoto-electrode of thephotomultiplier. In this way we again are dealing with internal radioactive sources, as with thegas counters. For higher-energy and g particles solid crystals are available made of organic (anthracene) or inorganic compounds (sodium iodide). Theresult is that each incoming particle causes alight flash in thescintillator, which can be seen by alight sensitive detector, thephotocathode. Thefact is that certain materials emit electrons when they are hit by a light flash, the so-called photoelectric effect. Thenumber of primary electrons is very small. Therefore, as with theproportional counter operation, amultiplication process 116

is needed. This is realised in aphotomultiplier tube (Fig.11.7). Each primary electron is accelerated and able to cause theemission of additional secondary electrons in thesecond electrode plate or dynode at ahigher positive voltage. This process is repeated several times, so that finally an electric pulse arrives at thelast dynode that is easily measurable. Also here the final pulse is proportional to themultiplication factor adirect function of thevoltage and theenergy of theincoming particle. This allows theselective registration of only those particles that originate from theradioactive decay event of interest (such as 14C or 3H). 11.3.2.2. Counter operation In Sect.11.2.4.2 we have mentioned thepreparation of benzene from CO2 via acetylene. Typical quantities being treated are 1 to 10grams of carbon, resulting in 1.2 to 12mL of benzene. Thescintillation light emitted by excited C6H6 does not have thefrequency for which thephotocathode in themultiplier tube is sensitive. Therefore, certain high-molecular compounds are added in order to shift thefrequencies to lower energies. Generally alarge number of samples is arranged in aliquid scintillation spectrometer or counter (LSS), in which thesamples are in turn placed in front of thephotomultiplier automatically. Also here arrangements have been made to reduce thebackground radiation as much as possible, primarily by using an anti-coincidence arrange-

measuring techniques

photocathode

particle from radioactive decay

secondary electrons

photomultiplier

ties attempts have been successful to detect single C particles in carbon and separate these from other foreign elements.
14
output signal

scintillator dynodes at increasing high voltage

light

primary electrons

Fig. 11.7. Schematic drawing of a (liquid) scintillation counter, the detector part of the LSS. An electron from - decay in thescintillating crystal or liquid causes alight flash that is transformed into electrons at thephotocathode; thenumber of primary electrons is multiplied by secondary emitting dynodes at increasing high voltage.

IRMS operates at afew kV and accelerates molecules such as CO2, which are separated into ion beams of masses 44, 45 and 46. For 14CO2 themass is 46 which signal due to its extremely low abundance of < 1012 is completely lost in the46 signal from thevarious stable isotopic combinations in CO2. It appears that, by making thestep to C ions instead of CO2 ions, theisobar problem can be solved. This means accelerating over MV rather than kV. Under these high-voltage conditions registration becomes possible in anuclear particle detector. Contrary to IRMS single particles can then be detected, rather than beam currents. For this purpose existing nuclear accelerators were used, specifically Tandem Van de Graaff Accelerators. Later dedicated machines were constructed and put into operation that are much smaller (Fig.11.8) [112]. Thecomplete set-up of theaccelerator with surrounding equipment is called Accelerator Mass Spectrometer (AMS). Theessential features of an AMS are thefollowing: (1) In theion source negative ions are produced. This is necessary because contamination of carbon by nitrogen can not be avoided and aN+ ion beam would make thedetection of 14C practically impossible, 14C having thesame position in theultimate mass spectrum. Negative ions, on theother hand, have theadvantage that N- ions are extremely unstable and loose their charge before entering theaccelerator. (2) Thenegative ions are produced by bombarding graphite i.e. thesample with Cs atoms. Presently, only very few CO2 ion sources are operational for AMS. This would be less aggravating for thechemical preparation procedures, but such asource is acomplicated device. (3) Ultimately, positive ions are more easily to detect, so that inside theaccelerator thenegative electric charge of thecarbon ions is removed and replaced by apositive charge by steering theions through astripper gas (Ar). Thestripping process especially destroys molecular isobars with mass 14, such 117

ment of other scintillation counters (instead of theuse of GM counters with PGC). Theadvantage of theLSS is that it can be purchased automated and purchased commercially, while agas counter set-up has to be made by thelaboratory. On theother hand, theoperation of aPGC is more transparent, from aphysical point of view. In principle thesame type of calculations lead to theactivity of thesample, as shown for thegas counters (Eqs.11.21 and 11.23). Related to theproblem of gas purity with thegas counters, liquid scintillation may suffer from impurities in thebenzene + scintillator mixture. This results in adecrease of thesize of theelectric output pulse. For this effect of quenching acorrection is to be applied. 11.4. Mass spectrometry for lowabundance isotopes 11.4.1. Principle and application of AMS Detecting thepresence of isotopes with avery low abundance such as theradioactive isotopes, for instance 14C in carbonaceous material, wood, charcoal, peat, bone, shells, groundwater, by detecting the radioactive decay is very inefficient. Of all 14C present in asample only one thousandth decays in about 8 years, i.e. 3.81012 part per sec. Amuch more efficient detection method is mass spectrometry, i.e. measuring theactual concentration of 14C. Nevertheless, only in thelate seven-

INTRODUCTION

as thebeam contaminants 13CH and 12CH. Thenow positive ions are again accelerated and subsequently mass selected in amagnetic field so that 12C, 13C and 14C can be detected separately. (4) Before entering theaccelerator, theions are mass separated by a magnetic field and the12C beam is reduced by afactor of 100 by afast rotating diaphragm (chopper, Fig. 11.8). Thesecond magnet recombines thethree ion beams. Thespecial advantages of theAMS technique, in comparison with radiometry, are that: (1) only milligram (or smaller) quantities of carbon are needed for one analysis, compared to roughly grams for theradiometric techniques (see Table11.3) [113]; (2) theanalysis is considerably faster, i.e. lasts an hour instead of days. Thedisadvantages are that: (1) thecapital investment is almost 100 times larger; (2) theAMS technique is more complicated from atechnical point of view; (3) theprecision is not yet as good as thebest counters (PGC or LSS) can manage (Table11.4).

11.5. Reporting 14C activities and concentrations 11.5.1. Thechoice of variables Thefollowing definitions are in use: Theabsolute (specific) 14C activity, that is the14C radioactivity (in Bq or, conventionally, in disintegrations per minute (dpm) per gram of carbon) is given thesymbol
14

A (in dpm/gC)

(11.29)

In general, 14C laboratories are not able to make an absolute measurement, because themeasuring efficiency is unknown. Also, in general, theabsolute 14C content of asample is generally not relevant. Therefore, thesample activities are compared with theactivity of areference material, theinternational standard. In reality, thenumber of 14C registrations ( registrations from 14C decay in radiometric detectors such as proportional counters and liquid scintillation counters, registrations of 14C concentration in AMS systems) are related to thenumber of registrations from thereference sample under equal conditions. This results in theintroduction of a14C activity ratio or 14 C concentration ratio:
14

a=

measuring efficiency 14 Asample measuring efficiency Areference

14
14

14

Asample

14

Areference
14

accelerator 0

C decay rate in the sample = 14 0 C decay rate in the ref . material

magnet
12

14

C concentration in th C concentration in the re

magnet

chopper magnet ion source

very high voltage

C and 13C detectors

14

C detector

5 10 m

Fig. 11.8. Schematic and simplified drawing of an Accelerator Mass Spectrometer (AMS) [112]. Theion source produces negative carbon ions. In order to reduce theoverwhelming contribution of 12C, thenumber of C ions are artificially reduced by afactor of 100 in thechopper. TheC- ions are accelerated in theaccelerator tube of theleft half of theaccelerator by an electric field of about 3 MV. In themiddle they are stripped of electrons to C3+, so that in theright half, they are further accelerated as positive ions. In thefinal magnet the12C, 13C and 14C ion are separated and finally counted.

118

14

a=
14

measuring efficiency 14 Asample measuring efficiency Areference Asample

14

14

Asample

14

Areference measuring techniques

14

ncy 14 Asample
14

In several thedifferences in 14C content C concentrat ion in cases the sample 14 between samples are small. Therefore, theuse C concentrat ion in the ref . material of relative abundances has been adopted from 14 in the sample C concentration in the sample the stable-isotope field, in casu the relative 14C = 14 he ref . material C concentration in the ref . material content (activity or concentration), 14, defined as thedifference between sample and standard 14C (11.30) content as afraction of thestandard value: Because in thenumerator and denominator of the last two fractions, the detection efficien(11.31) cies are equal for sample and standard, whether theanalytical technique applied is radiometric or mass spectrometric. Thevalues of are small numbers and thereTheuse of theratio 14a is adequate for any type of measuring technique. Henceforth, thesymbol 14A will be used for the14C content, radioactivity as well as concentration, Under natural circumstances thevalues of a are between 0 and 1. In order to avoid alarge number of decimals, it is general practice to report these values in % (percent), which is equivalent to 102. Therefore, thefactor 102 should not enter into equations (as 14a/102).
14

cy Areference

14

= Areference 14 C decay rate in the sample = 14 = C decay rate in the ref . material

fore generally given in (permil), which is equivalent to 103. Therefore, thefactor 103 should not enter into mathematical equations (as /103).

A14C reference material or standard was chosen to represent as closely as possible the14C content of carbon in naturally growing plants. The14C content of thestandard material itself does not need to be, in fact is not, equal to thestandard 14C content. Thedefinition of thestandard 14C activity is based on thespecific activity of theoriginal NBS oxalic acid (Ox1) [78], as will be discussed in more detail.

TABLE 10.4. Survey of specific features of thevarious isotopic techniques.

Rare isotopes
2

Medium type

Medium quantity few mL gas to few 0.1mL gas few mL H2O few 100mL H2O 150L CO2 (equiv.) few mL H2O few 100mL H2O few to 15mL C6H6 0.12 mg C few mL CO2

Precision H: 0.1 C: 0.01 18 O: 0.02 15 N: 0.02

2 13

IRMS

H, 13C, 18O (15N, 34S)

3

H2, CO2, N2 H2, C2H6 with enrichment CO2, C2H2, C3H8 H2O C6H6 C (graphite) (CO2)

H C

PGC
14 3

1 TU (NE) 0.1 TU (E) 0.50.1% * few TU (NE) few 0.1 TU (E) 0.50.2% * 0.5% * ?

H C C

LSS
14

AMS

14

* for carbon with 14a=100% Note: The3H and 14C precisions quoted are valid for samples of roughly 10 TU and present-day activities, respectively. Theasterisks refer to thecases where larger quantities of sample allow greater precision. For theradiometric techniques we have assumed acounting time of one or two days. IRMS=Isotope Ratio Mass Spectrometer LSS=Liquid scintillation spectrometer PGC=Proportional Gas Counter AMS=Accelerator Mass Spectrometer

119

, , ililyyaad navons navonsaucune aucunepreuve preuveexprimentale exprimentalefiable fiablede dela lavraie vraievaleur valeurde de

croire croireque quela lavraie vraievaleur valeurde deest estproche prochede de1,9 1,9, ,et etparce parceque quecette cetteincertitude incertitud

14 C, C,nous nousutiliserons utiliserons de degrandeur grandeurde dela laprcision prcisionanalytique analytiquedes desmesures mesuresde de14 INTRODUCTION approximation approximationsuffisante. suffisante.

11.5.2. Thestandardisation

11.5.2.2 11.5.2.2

11.5.2.2. Thequestion of radioactive decay LE LE PROBLEME PROBLEME DE DE LA LA DECROISSANCE DECROISSANCE RADIOACTIVE RADIOACTIVE

For radioactive samples ameasured activity deBefore the definition of standards can Pour be com -chantillons Pour les les chantillons radioactifs, radioactifs, lactivit lactivit mesure mesuredpend dpenddu dutemps tempsde demesure, mesure pleted, two factors have to be discussed that pends on thetime of measurement, tm: complicate thestandardisation of 14C results and 1414 ( t )0 ) tt 0 0 ( mt 0t AA (t(m tm )) ==1414 AA (t(0t) )e ou ou AA ==1414 AA ee tm or 1414 0e therespective symbols. (11.33) ce cequi quiest estgalement galementvalable valablepour pourle lematriel matrielstandard. standard.Ainsi, Ainsi,quand quandon onrepor repo 11.5.2.1. Thequestion of isotope fractionation14 which is also valid for thestandard material. 14doit C, C,lanne lanne pour pour laquelle laquelle la la valeur valeur est est correcte correcte doit tre tre spcifie. spcifie. La La m m absolue absolue 14 Therefore, when reporting an absolute C conDuring thetransition of carbon from one comgalement galementvraie vraiepour pourle lestandard. standard.Lanne LanneAD1950 AD1950aat tchoisie choisiecomme commeanne ann pound to another, i.e. theassimilation of CO2 by 0 0 tent, theyear for which thevalue is valid must be specified. same is true for the standard. serfre rfre donc doncThe cette cette "anne "anne 0". 0".Lactivit Lactivit standard standardest estdonc doncvalable valab lexposant lexposant to sur- se plants, theexchange of CO2 from theair Theyear of reference was chosen to be AD1950; 14 14 face water, etc., isotope fractionation occurs Cdes deschantillons chantillonsse serduit rduitavec avecle letemps tempssimult simu 1950. 1950.for Comme Commela lateneur teneuren en C thesuperscript 0 refers to this year 0. Thestan13 14 14 C as well as for 14C. Also thelaboratory treatCentre entreles lesdeux deu celle celledu dumatriel matriel standard, toute toute comparaison comparaison de dela lateneur teneur en en dardstandard, activity thus is valid for theyear 1950. As C ment of sample materials may introduce an isoto14 ). valable valablepour pourlanne lanne 1950 1950(= (= t0t). 0samples the C content of reduces in time simulpic change, for instance by an incomplete chemitaneously with thestandard material, any com14 14 cal reaction. If this fractionation were neglected, La Laconsquence consquence est estbetween que quela lateneur teneur C C absolue, absolue, qui qui estbase basesur surla lacompar compa 14 est parison thetwo results in a C content samples of different chemical composition (carstandard standardAcide Acide Oxalique Oxalique selon selon des desprocdures procdures standardises, standardises,est estvalable valablepour pour valid for theyear 1950 (= t0). bonate and plants, C3 and C4 plants) but made of sans sans tenir tenir compte compte de de la la date date de de mesure. mesure. thesame (age) carbon (determined by atmospheric CO2) would seem to have different ages. Theconsequence is that an absolute 14C con14 tent, which is based on14 acomparison Therefore, in order to make 14C ages comparable, 11.5.2.3 11.5.2.3 D D EFINITION EFINITION DE DE L L ACTIVITE ACTIVITE C C STANDARD STANDARD with theOxalic Acid standard according to stanacorrection has to be applied for this fractionNous Nous pouvons pouvons maintenant maintenant dfinir dfinir lactivit lactivit standard standard 95% 95%de delactivit lactivitdu du Techniques de Mesure 14 dard procedures, is valid for theyear 1950, ation effect. Thetheoretical relation between C 13 irrespective of thetime of measurement. dAcide dAcideOxalique Oxalique nr.1 nr.1(Ox1) (Ox1) dans dans AD AD1950: 1950: and C fractionations is written as (Eq.3.43):
14

00 (11.32) AA == 00 ,95 ,951414 AA 13 13 ,56 ,56 00 ,07 ,07 dpm/gC dpm/gC == 00 ,226 ,226 00 ,001 ,001 Bq/gC Bq/gC Ox Ox 1N 1 N== 14 11.5.2.3. Definition of the C standard activity 14 13 14 where A and R refer to themeasured, A14 N to 14 13 14 14 14 o A et thefractionation-corrected R se rfrent lactivit or Cnormalised mesure, A corrige du N lactivit C We can nowC define the standard activity as 95% 13 13 13 13 R (or rather ) is an interactivity, while fractionnement ou normaliseN , tandis que R N ) theactivity est une valeur standard batch of Oxalic Acid N N (ou plutt of of thespecific 13 nationally adopted standard value. value nr.1 (Ox1) AD 1950: N =This 25 versus VPDB (Eq. in 7.1.3). Lactivit internationalement adopte. Cette valeur est 7.1.3). Also is 13N=25 versus VPDB (Eq. standard doit tre normalise de la mme faon. La seule . . . . thestandard activity has to be normalised inexception est. que pour des 13 raisons historiques way. le vieux Acide. Oxalique thesame Theonly exception is that -for est normalis . standard . (Ox1) . . sa valeur (11.34) Chapitre 11 historical reasonstheold Oxalic Acid standard relle de 19. 13 Chapitre 11 of 19. (Ox1) is normalised to its real value where R stands for Reference, N for Normalised 13 for isotope fractionation (to 13=25, Toutes les valeurs 13 de sont exprimes par rapport au standard VPDB (Gonfiantini, 1984). o R correspond "Rfrence", N "Normalis" pour leonly fractionnement isot 13 All values are with respect to theVPDB in thecase of Ox1 to =19) 13 and dpm/gC oprocessus R correspond "Rfrence", N "Normalis" pour le fractionnement isotopique (avec standard [41]. Pour les naturels, la valeur de est denviron 2 (Craig, Puisque nous means 1954). disintegrations per minute per gram of car0 bon, while navons aucune preuve exprimentale fiable de la vraie valeur de , il y thesuperscript a des raisons de refers to thefact that For natural processes thevalue of is about 2 thedefinition is valid for theyear AD1950 only. croire que la vraie valeur de estno proche de 1,9 , et parce que cette incertitude est de lordre [28]. Since we have reliable experimental eviThedefinition by Eq.11.34 is related to 14 thetrue value of , there are de grandeurdence de la about prcision analytique des mesures de reaC, nous utiliserons presented = 2 comme time by: sons to believe that thetrue value of may be approximation suffisante. closer to 1.9 , and because this uncertainty is 14 A 14 A0 e ( ti t0 ) 0.95 14 A0 e (ti t0 ) 0.95 14 A RN RN Ox 1 N Ox 1 N irrelevant compared to theanalytical precision of ( ti t 0 ) ( ti t 0 ) 14 14 0 14 0 14 14 PROBLEME ARN ARN ewill use 0. 95RADIOACTIVE AOxa e 0.95 AOx1 N (11.35) (11.35) 11.5.2.2 LE DE LA DECROISSANCE 1N C measurements, we =2 as suffi cient approximation. Pour les chantillons radioactifs, lactivit mesure dpend du temps de mesure, ti: refer to theyear 1950 and to where t0 and tm themoment of theorigin of thesample, respec14 tively. (11.33) A(t ) = 14 A(t ) e t ou 14 A = 14 A 0 e ( tm t0 )

AN 13 RN = 13 14 A R

(11.32)

14 14 0 0 RN RN

ce qui est galement valable pour le matriel standard. Ainsi, quand on reporte une teneur lanne pour laquelle la valeur est correcte doit tre spcifie. La mme chose est absolue 14C,120 14 0 0 AOx 2 N anne (1.2736 0.0004) 14 AOx galement vraie pour le standard. Lanne AD1950 a t choisie comme de rfrence; 1N 14 0 14 0 0 ( 1 1 . 3 6) AOx 2 N (1.2736 0.0". 0004 ) AOx1 Nstandard est donc valable pour lanne cette "anne Lactivit lexposant se rfre donc 14 1950. Comme la teneur en C des chantillons se rduit avec le temps simultanment avec

= 25, avec 13 = 19 seulement pour Ox1) et dpm/gC dsintgrations moyennes par 13 0 e", N "Normalis" le fractionnement isotopique (avec 13nest se rfre au fait que la dfinition parpour gramme de carbone, que lexposant o R minute correspond "Rfrence", N tandis "Normalis" pour le fractionnement isotopique (avecTechniques de Mesure seulement valide pour Ox1) et dpm/gC dsintgrations moyennes par que pour lanne AD1950. 13 de Mesure = 25, avec 0 = 19 seulement pour Ox1) et dpm/gC dsintgrations moyennes Techniques par nest ne, tandis que lexposant se rfre au fait que la dfinition 0 measuring techniques La dfinition prsente dans lEq. que 11.34 est relie au par: setemps rfre au fait que la dfinition nest minute par gramme de carbone, tandis lexposant standard dtermine avec le mme rendement de dtection, environ la m 950. ( ti t 0 ) ( ti t 0 ) 14 14 0 14 0 14 valide que pour lanne AD1950. ARN ARN e 0.95 AOx1 N e corrige 0.95 A (11.35) standard dtermine avec le mme rendement dtection, environ les la m 1 N fractionnement isotopique. de pourOx14 le Dans ces conditions, r ( ti t 0 ) ( ti t 0 ) 14 14 0 14 0 A = A e = 0 , 95 A e = 0 , 95 A (11.35) lEq. 11.34 est relie au temps par: RN RN Ox 1 N Ox 1 N corrige pour le fractionnement isotopique. Dans ces conditions, les r Because theoriginal of relie oxalic has diffrents La dfinition prsente dans lEq. supply 11.34 est auacid temps par:laboratoires deviennent comparables. La dcroissance des conce Theconsequence measurediffrents deviennent La dcroissance des conce been exhausted, anew batch of oxalic acid (Ox2) laboratoires ettherelative tm est reprsente par lEq. 11.33. lchantillon et du standard entre of t0 comparables. ( ti t 0 ) ( ti t 0 ) 14 0 14 14 ment is that theresulting value of a does = 0,95 e = 0 , 95 A (11.35) o tA et t se rapportent, respectivement, lanne 1950 et la date dorigine de lchantillon. 0 Ox ( ti tOx ((formerti t 0 ) 14 0 0 is available for by14theNIST 1 Ni lchantillon du standard entre(11.35) t0 et tm est reprsente par lEq. 11.33. 0 ) 1N ARN = 14 ARN edistribution = 0,95 AOx = 0,95 14 et A 1N e Ox 1 N depend on thetime not measurement La mesure relative a pour consquence de of donner une valeur 14a indpendant ly US-NBS). 14 Comme le stock dacide oxalique dorigine est puis, un nouveau lot dacide oxalique (Ox2) A value (see 14a indpendant is, contrary to theabsolute 14 donner une valeur La mesure relative a pour de consquence la mesure, au contraire la valeur de A absolue (voir Part. 11.5.2.2); l ctivement, lanne 1950 et la date dorigine de by lchantillon. Through careful measurement anumber of est disponible auprs du NIST (anciennement US-NBS). Sect. 11.5.2.2); theabsolute activity result14 o t0 et ti se rapportent, respectivement, lanne 1950 et la date dorigine dede lchantillon. la mesure, au contraire la valeur A absolue (voir Part. 11.5.2.2); l 14 obtenue la mesure relative est valide pour lanne ingde from therelative measurement is valid for 1950, si on la mu laboratories [79], the Cdacide activity has become re- partir ique dorigine est puis, un nouveau lot oxalique (Ox2) A la mesures soigneuses ralises par plusieurs 1983), onest a reli obtenue laboratoires partir dedacide la Mann, mesure relative valide pour Bq/gC: lanne 1950, si on la mu 14 14 oxalique Comme le suite stockde dacide oxalique dorigine est puis, un nouveau (Ox2) 1950, if multiplied by 0.226 Bq/gC: a theyear lot 0,226 = A0 (Bq/gC) to that of theoriginal Ox1 by: T (anciennement lated US-NBS). 14 14 14 14 14 0 0 lactivit C celle de lOx1 original par: 0.226= (Bq/gC). Bq/gC: a a0,226 = A A (Bq/gC) est disponible auprs du NIST (anciennement US-NBS). 14 0 0 (11haut, .36) dans certaines tudes sur les systm AOx 214 .2736 0.0004 ) 14 A (11.36) Comme cela a t envisag plus N 0 (1 Ox 1 N uses ralises par plusieurs laboratoires Mann, 1983), on a reli 14 0 As was anticipated above, certain studies on natu(11.36) AOx 2 0,0004)par A A la suite de mesures soigneuses plusieurs laboratoires Mann, 1983), on a 14 envisag N = (1,2736ralises Ox 1 N Comme cela a t plus haut, dans certaines tudes sur leshabitu systm C prsentent des reli carts faibles. Dans ces cas, il est concentrations original par: 14 Contrary to theOld Oxalic acid (with atrue 13 ral en systems are concerned with only small differ 14 lactivit C celle de lOx1 original par: 1413 en C prsentent des carts faibles. Dans ces cas, il est habitu concentrations C content. In those cases it entre is convenences in 14 Csous forme diffrence relative lactivit mesure de valeurs Contrairement acide oxalique (avecles une valeur14 relle de de 19.2, H.Craig, 0 value of lancien 19.2, H.Craig, pers.comm., [79]), (11.36) 6 0,0004) 14 AOx 14 1N C sous forme de diffrence relative entre lactivit mesure de les valeurs C data as therelative difference tional to report 13 14 0 14 0 celle de la rfrence: Ox2 = 17,6) a t normalis comm. pers. 1983), le nouvel (avec (11.36) (= AOx 2Mann, (1,2736 0 ,(with 0004 )13acide AOx theNew Oxalic acid = 17.6) has Ox2 N = 1 N oxalique between themeasured sample activity and that of 13 celle de la rfrence: 13 topour be for isotope fracide oxalique (avec unenormalised valeur (=corrected relle de 19.2, = 25, tandis que les deux activits se corrig le fractionnement isotopique) H.Craig, 14 H.Craig, Contrairement lancien oxalique (avec une valeur 13 thereference: relle 14 de 13 13acide tionation) to =25, while both activities A 19.2, A0 14 14 = 17,6) a t normalis (= nouvel acide oxalique (avec rfrent AD1950. Ox2 14 14 0 1= 1 = = a 1 13 14 A a t normalis 14 A0 refer to AD1950. (= comm. pers. Mann, 1983), le nouvel acide oxalique (avec 14 17,6) 14 13 Ox2 = = 14 AR 1 = 14 AR 1 = a 1 ent isotopique) = 25, tandis que les deux activits se (11.39) 0 Par consquent, lactivit standard est: 13 A AR R deux activits = 25, tandis que les se corrig pour le fractionnement isotopique) Consequently thestandard activity is: 14 13 0,95 rfrent 14 0 AD1950. 0 14 indiqu, normaliser rsultats C partir de lcart As mentioned, it les has(11.37) become common practice to entre 13 mes 0 ,95 0.7459 14 AOx ARN14Comme 0.7459 14 AOx 0 14 14 2 N 0 or 2N 14 ndard est: ARN 14 A AOxnormaliser A = = 0,7459 AOx 2 N or (11.37) 14 Comme indiqu, les Maintenant, rsultats C la partir de lcart entre mes 1. 2736 RN RN = 0,7459 2 N courante. normalise C results for deviations of themeadevenu une pratique discussion sur la procdure d Par consquent, lactivit 1,2736standard est: 13 13 12d from 25. Now thediscussion of sured devenu une pratique courante. Maintenant, la discussion sur la procdure peut tre complte. Dans la mesure o, par convention, les valeurs de C/ 0 14 12 thenormalisation procedure can be completed. 9 14 AOx or 14 ARN = 0,7459 AOx 2 N (11.37) (11.37) peut tre international complte. Dans la mesure o,stables, par convention, les valeurs de 13C/ 2N 14 0 0,95 de A pour standard pour les isotopes Vienna PDB, lEq. 11.32 peu 13en 12 14 les 0 14 0 Ox1 et Ox2 14 14 Since o valeurs se rfrent lactivit du matriel 1950, C/ C values are related ARN = = 0,7459 AOx 2 N or ARN = 0,7459 international AOx 2 N conventionally (11.37) standard pour les isotopes stables, Vienna PDB, lEq. 11.32 peu 1,2736 14 la manire suivante: to theinternational standard for stable isotopes, indpendamment de 0 lpoque de la mesure. refer to where the A values for Ox1 and Ox2 la manire suivante: Vienna PDB, Eq.11.32 can be rewritten by: r Ox1 et Ox2 theactivity se rfrent of lactivit du in matriel en 1950, thematerial 1950, irrespective 2 14 0 14 14 matriel 13 o les valeurs de A pour Ox1 et Ox2 se rfrent lactivit 1950, e de la mesure. 11.5.3 DERNIERES DEFINITIONS AN / du ARN 13 Ren RVPDB 2 of thetime of measurement. N/ 14 14 13 = 14A / 14 A 13R / 13 R 13 indpendamment de lpoque de la mesure. N RN N VPDB A/ ARN R/ RVPDB 14 = Nous pouvons maintenant dfinir plus prcisment la concentration en C dun chantillon en 13 14 14 13 ARN R/ RVPDB NITIONS termes de rapport dactivit ou rapport de concentration A/ 13 comme le rapport entre la 11.5.3. Final definitions or using Eq.11.38, with N=25, and conse13 11.5.3 DERNIERES DEFINITIONS 14 13 ou en utilisant lEq. 11.38, avec = 25, et par consquent 1 + 13N = N finir plus prcisment la concentration en C dun chantillon concentration en carbone-14 mesure et la valeur standard (qui doit toujours tre normalis =1 + ( 25)=0.975: quently 1 + 14 duen N 13 We can now more carefully specify the ou C en conutilisant lEq. N = 25, et par consquent 1 + 13N = 14 11.38, avec 13 0,975: t ou rapport de concentration comme le rapport entre la Nous pouvons maintenant dfinir plus prcisment la concentration en C dun chantillon en ), les deux termes se rapportant la date de la mesure: pour tent of asample in terms of theactivity ratio or . 0,975: mesure et la de valeur du standard (qui as doit toujours tre termes rapport dactivit ou rapport de normalis concentration comme le rapport entre la concentration ratio theratio between themea. 2 2 2 14 0 14 14 0 (tm t0 ) 13 14 A mesure A e A standard sured content and thevalue of thestandard 2 14 1 + (25 ) 2 14 0,975 2 concentration en et la valeur du normalis rapportant la date de carbone-14 la mesure: 14 0 (qui 14 C 14 doit toujours 14 1 + tre N a = 14 = 14 0 (tm t0 ) = 14 13 = a 13 aN = a a (25 0 13 1 = (11.38) = 14 a 10 ,975 . (which always has to be normalised mesure: ), with 14 14 1 + A ARN ARN e la datefor 1+ N 1 + 13) + + 13 deux termes se de la pour 13), les RN rapportant = a a N = 14 a a = (11.40) 13 13 13 0 (tm t0 ) 0 14both referring to thetime of measurement: 1+ 1 + 1 + A e A terms 14 0 = 14 0 = a (11.38) ) 0 14 t0 ) 14 0 14 14 0 (tm A ARN e (tm t0 o t0 correspond lanne A lactivit de 0lchantillon mesure au temps tm, et 14ARN A A 1950, e A RN et mme: 14 de 14 and likewise: a = 14 = = 14 0 = a (11.38) . (tm t0 ) 0 et de mme: avec1413 = 19 ou A 0,746 14 A avec 13N = 25) la valeur du (= 0,95 14A ARN A Ox1 N e Ox2 RN RN . 2 50, 14A lactivit de lchantillon mesure au temps tm, et 14ARN (11.41) (11.38) 0,975 2 14 14 14 13 A A = 204 ou 14 14 204 N 13 = 19 0,746 A avec = 25) la valeur du ,975 Ox2 N A . lactivit o t0 correspond t lanne 1950, mesure au temps 14 de lchantillon 14 10 tm, et ARN + where A is theacAN = 14 A 0 refers to theyear 1950, 1 + 13 14 13 14 13while into: AOx1 avec N = 19 ou 0,746 AOx2 avec N = Eq.11.39 25) la valeur du (= 0,95 tivity transforms of thesample measured at time tm, and 14 14 13 ARN (=0.95 AOx1 with N=19 14 tandis or que lEq. transforme en: N 11.39 = 14aN se 1 (11.42) 14 13 204 0.746 AOx2 with N=25) is thevalue tandis of que lEq. 11.39 se transforme en: thestandard determined with thesame detection 14 = 14a 1 N N 11.5.4. Special cases efficiency, at about thesame time tm and corrected 14 N = 14a N1 for isotope fractionation. In this way 14a results In general thepresentation of 14C results depends from different laboratories become comparable. on thetype of application. For each case an exThedecay of sample and standard 14C content ample is given to illustrate theapplicable definifrom t0 to tm is described by Eq.11.33. tions and equations.

121

Chapitre 11

11.5.4 CAS PARTICULIERS

14

INTRODUCTION

H a , thenon-normalised 14C content at thetime 14 a = 14aN [(1 + 13) / 0.975]2 = 0.549 = 54.9% of sampling, is themost meaningful, than 14rather S 14 [cf. 11.40] Du point de gochimique lutilisation de a , la concentration C non normalise Techniques de Mesure a vue value. Instead of applying anormalisation lpoque decorrection, lchantillonnage, est14la logique, plutt quune The valeur 14 . Au lieu dappliquer theinitial C plus content of groundwater C content in theyear of sampling (1998) 14 is going to be determined by specific geochemi une correction de normalisation, la concentration initiale en C de leau then is: En hydrogologie onsouterraine sintressedoit la tre concentration en 14C de lchantillon d cal reasoning of theorigin of theinorganic car14 dtermine partir dun raisonnement gochimique spcifique sur lorigine de lala de lchantillonnage. a doit tre d normalise : 14 S 13 bon content. Furthermore, if we are dealing with a = 14aNCest [(1 + pourquoi, ) / 0.975]2valeur exp[(1998 1950) concentration en carbone inorganique. Par ailleurs, si on sintresse lge des eaux groundwater ages, it is irrelevant from ahy14 13 54,6 % 2 / 8267] = 0.546 a = 14de a [(1 + = )lge / 0,975] N savoir souterraines, il est sans intrt dun de vue si doit = 0,549 = 54.9 % drological point of view point whether ageshydrologique count 14 S in time from theyear of sampling (calcutre comptback en temps coul partir de lanne de lchantillonnage bas sur ) ou La concentration en 14 C pour lanne de lchantillonnage (1998) est alors: ( (calcul 54.6 pMC=% ofamodern carbon=%MC) 14 S lation based on a14 ) or 14 from 1950 (calculation 0 14 [cf. 11.43] partir de 1950 (calcul 14 bas sur a = a ). De fait, la prcision des datations C de routine est 14 S based on a=14a0). Moreover, theprecision of a = 14aN [(1 + 13) / 0,975]2 exp[(1998 1950) / 8267] = 0,546 14 de toute faon de 50 ou plus. Enyears consquence, on peut de manire quivalente utiliser la routine C ans dating is 50 or more anyway. Using more or less sophisticated models, the14C 14 13 pMC = % de carbone moderne = %MC) ( 54,6 Consequently, we can equally well use themost de laboratoire simples. valeur a la plus simple en % comme celle obtenue par les procdures and the C data, together with information on simple 14a value in % as is obtained in simple labthechemical composition of thewater sample, A laide de modles plus ou moins sophistiqus, les donnes 14C 13C oratory procedures. can be used to estimate thesample age (i.e. informations sur la composition chimique de lchantillon deau, peuvent 13 13 theperiod of time since theinfiltration of thewaWithout C, C le normalisation, theactivity ratio in Sans normalisation rapport dactivit de lanne dchantillonnage est: estimer lge de Astraightforward lchantillon (i.e. la priode de temps coule ter). water age as obtained by depuis linfiltra theyear of sampling is: simply applying Eq.11.52 is not possible. 2 Obtenir directement un "ge de leau" en appliquant simplement lEq. 1 + 13 ( ts 1950 ) / 8267 14 S 14 a = aN (11.43) (11.43) e 0,975 possible. 11.5.4.2. Oceanography and atmospheric research 11.5.4.2 RECHERCHE EN OCEANOGRAPHIE ET SUR LATMOSPHERE Souvent ces valeurs sont donnes en given pour cent de carbone (pMC) ou pourcent de theoceanographic Thesame equation holds for Often these values are in percent of moderne 14 S La mme quation est retenue pour ocanographiques. T applications. However, as thespread of thedata modern carbon (pMC) modern moderne (pM). De plus bpM/100 (= or a )percent est parfois appel fraction moderne. Cependant, les le applications 14 S generally ispour quite small, it is common practice to In addition pM/100 a ) is somelventail des donnes est gnralement faible, on a lhabitude de prse symbole pM (pM). est utilis par les hydro (= chimistes et les ocanographes exprimer laassez times called fraction modern. However, report the14C data as relative numbers,14 i.e. as de14 C sous similaires forme de nombres relatifs, de valeurs corriges pour la dcroi picoMole. Cest pourquoi, pcm, pCM, pM, et les variants ne devraient pasi.e. tre thesymbol pM is in use by water chemists cay corrected 14 values: utilises: lexpression % est approprie si elle est associe un symbole bien dfini. 14 and oceanographers as picoMole. Therefore, A 14 S 14 S = a 1 = 14 1 pmc, pMC, pM, est anddevenue similar variants should Nanmoins, lutilisation pCM si habituelle, quil est difficile dviter cette (11.44) 0 unit. ARN not be used: % is adequate in combination Toutefois il parat plus raisonnable dutiliser le symbole %CM au lieu de pCM. with a well-defined symbol. Nevertheless, Inles general results aregalement also corrected for isotope En gnral, rsultats sont corrigs pour le fractionnemen theuse of pMC has become so established, fractionation (=normalised): normaliss): that this unit is difficult to avoid. However, Exemple: leau souterraine . it seems more reasonable to use thesymbol Lactivit mesure et instead normalise ou rapport de concentration est : 2 %MC of pMC. ( t s t0 ) / 8267 0,975 14 S 14 S 14 N = a N 1 = a e 14 1 + 13 1 (11.45) aN = 0,537 = 53.7 % Example: groundwater 13 La valeur mesure sur le carbone total (comme celleThese obtenue par la equations areprocdure used to express the14C con14 Themeasured and normalised activity or concenCes quations utilise pour exprimer as la well teneur en atmoC dchantillons iss tentsont of samples of oceanwater as of dextraction) est: tration ratio is: spheric CO . leau ocanique que du2CO2 atmosphrique. 13 14 = 13,82 aN = 0.537 = 53.7 % 11.5.4.2.1. Example: oceanic DIC and atmos11.5.4.2.1 ocanique et CO2 atmosphrique con- Exemple: CID Themeasured 13 value of thetotal carbon pheric CO2 tent (as is obtained by theextraction procedure) 14 The14C content resulting from aroutine measureLa concentration en C issue dune mesure de routine implique une no is: 206 13 13 ment includes normalisation to =25: = 25: 13 = 13.82 (1) deep-ocean bottom water DIC (=dissolved a) le CID (= Carbone Inorganique inorganic carbon): Dissous) dune eau profonde du fond de l In groundwater hydrology we are interested in 14 14 0 14 aN 14 0 aN = 0,872 = 87,2% the14C content of thewater sample at thetime of aN= = aN =0.872=87.2% [cf. 11.40]
14 YDROLOGIE S

En gnral la prsentation des rsultats C dpend du type dutilisation. Pour chaque cas on va donner un exempleHydrology pour illustrer les dfinitions et les quations que lon peut appliquer. 11.5.4.1. sample collection. Therefore, the14a value has to be de-normalised: From ageochemical point of view theuse of 11.5.4.1

do: 14N = 14aN 1 = 0,128 = 128

122

avec 13 = +1,55

Pour cette correction on doit de nouveau utiliser la priode

1 14 0 14 0

14

C correcte

= 1/8267a . Par ailleurs, A et a se rapportent 1950 et A et 14ai lan carbone contenu dans lchantillon.
measuring techniques

14 i

Pour les valeurs normalises et corriges pour lge nous pouvons maintenant
14

= 128 from which: 14N = 14aN 1 = 0,128 Chapitre 11 [cf. 11.42] Chapitre 11

i = 14 a i 1 =

Chapitre 11 14 with 13 =+1.55 1950 ) / 8267 Quand on corrige du fait que la teneur C obtenue lanne 1950 au 14 valide 0 ( ti pour 208 est A e pour lanne 14 ( ti 1950 ) / 8267 14 Chapitre 11 Quand on corrige du fait que la teneur C obtenue est valide = 1 =1950 a eau 1 When corrected for thefact that theresultlieu de lanne dchantillonnage (1990): 14 0 14 A 14corrige du fait que la teneur Quand on C obtenue lanne 1950 au lieu de (1990): ing Clanne contentdchantillonnage is valid for theyear 1950 in- est valide pourRN (11.48) 14 stead of theyear of sampling (1990): lieu de lanne dchantillonnage (1990): S corrige 14 Quand on du fait que la teneur C obtenue est valide pour lanne 1950 au = 14 a N exp[ (1990 1950 ) / 8267 ] 1 = 0 ,132 = 132 N 14 S 14 o ti ] est la date BC= (ngative) ou AD (positive)) et pour les valeurs normalises: = a exp[ ( 1990 1950 ) / 8267 1 = 0 , 132 132 lieu de lanne dchantillonnage (1990): N N (where ti is thedate BC (negative) or AD (posi14 S 14 N = = 0.132 a N exp[ (1990 1950) / 8267] 1 = 0,132 = 132 = 132% tive)) and for thenormalised values: 2 b) CO2 atmosphrique: 14 S 14 0,975 14 = i 132 i = a exp[ ( 1990 1950 ) / 8267 ] 1 = 0 , 132 atmosphrique: b) CO2 N (2) N atmospheric CO2: 1 = 14 a e ( ti 1950) / 8267 N = 14 a N 14 14 1 + 13. 1 [cf. 11.42] do: N = aN 1 = 0,253 = +253 b) CO2 atmosphrique: 14 14 N= a 1= 0.253 =+253 from 14 which: N = 14 a 1 =N0,253 = +253 [cf. 11.42] do: 13 b) CO2 atmosphrique: = 14N13 [cf. 11.42] =14 a7,96 0,253 = +253 [cf. 11.42] do:avec N1= (11.49) = 7,96 avec 13 14 14 14 14 13 with =7.96 = acorrige 1 = 0,253 +253 [cf. 11.42] do: C obtenue est valide lanne 1950 au partir dun chantillon dg Quand on du fait=que teneur N N Exemple: concentration enpour C atmosphrique avec = 7,96 14 14 Cau content from Example: atmospheric C obtenue est valide pour lanne 1950 Quand on corrige du fait que teneur 14 lieu dchantillonnage (1985): content is validbois for theyear theresulting 13 de lanne C caractris par les cernes sample : wood from = corrige 7,96 aveclieu C obtenue est valide pour aknown-age lanne 1950 au Quand on du fait que teneur 14 de lanne dchantillonnage (1985): 1950 instead of theyear of sampling (1985): atreering Le 14 rapport dactivit mesur i.e. lactivit par rapport 0,95 fois lactivit lieu de (1985): S corrige 14 lanne 14 dchantillonnage C obtenue est valide pour lanne 1950 au Quand du fait que teneur [cf. 11.45] on N = 14 a N exp[(1985 1950) / 8267] 1 = 0, 247 = + 247 14 S normalise de lacide oxalique: Themeasured activity ratio i.e. theactivity with + 247 [cf. 11.45] = a exp[ ( 1985 1950 ) / 8267 ] 1 = 0 , 247 = lieu de lanne dchantillonnage (1985): N =N +247% [cf. 11.45] 14 S =0.247 14 respect to 0.95 times themeasured and nor[cf. 11.45] 13 N = a N exp[(1985 1950) / 8267] 1 = 0,247 = + 247 14 14 0 14 14 atmosphrique il reste le problme de savoir si la correction C Pour les chantillons de CO 2 malised oxalic activity: With CO2 samples it remains prob- a = a =( A / acid ARN) = 0,4235 13 or = 42,35% 14 S atmospheric atmosphrique il reste problme de savoir si la correction C Pour les chantillons de CO 247 [cf. 11.45] N = 14 a N exp[ (1985 1950 ) / 8267 ] 1 = 0le ,247 = + 13 2 13 lematic whether C correction applied (actre applique (suivant lEq.the 11.40) est correcte. La valeur de mesure peut trs bien 13 13 savoir atmosphrique il reste le problme de si la correction C Pourapplique les chantillons de CO 14 14 0 14 14 2 13 mesure peut trs bien (suivant lEq.avec 11.40) est correcte. La valeur a=combustibles a =( A / A 0.4235 cording Eq.11.40) is correct. Themeasured de 13 RN) = issu deLe la biosphre ou au tre lieuor = 42.35% affecte par un to mlange du CO2 mesur dedes lchantillon: fossiles, 13 13 mesure peut trs bien tre applique (suivant lEq. 11.40) est correcte. La valeur de [cf. 11.38] value may very well be affected by theadmixture la biosphre ou combustibles fossiles, au par un mlange avec du CO atmosphrique ilde reste le problme de savoir si la correction C lieu Pouraffecte lesseul chantillons de CO2 2 issu du fractionnement isotopique, comme le suppose de des manire pas forcment valide 13 of biospheric or fossil-fuel CO of by iso13 issu de laLa biosphre des combustibles fossiles, auvalide lieu affecte par un mlange avec du CO 22,5pas 2, instead du seul fractionnement isotopique, comme le suppose de manire forcment 13 = mesure peut trs tre applique (suivant 11.40) est 2correcte. valeur ou de of bien thesample: Themeasured la procdure delEq. correction (Mook, 1980b). tope fractionation alone, as is the not necessardu seul fractionnement isotopique, comme le suppose de manire pas forcment valide la procdure de correction (Mook, 1980b). issu de la biosphre oudactivit des combustibles fossiles, au lieu affecte parily un valid mlange avec du CO2of Le rapport normalis de lchantillon est: 13 presumption thecorrection proce =22.5 la de correction (Mook, 1980b). 11.5.4.3 G EOCHIMIE duprocdure seul fractionnement isotopique, comme le suppose de manire pas forcment valide dure [114]. 14 2 of thesample is: 11.5.4.3 GEOCHIMIE Thenormalised activity ratio aN = 14 a [0,975 la / (1 0,0225)] = 0,4213 or = 42,13% 14 la procdure de correction (Mook, 1980b). Dans les tudes gochimiques, il est souvent ncessaire de connatre concentration C 11.5.4.3 G EOCHIMIE 14 11.5.4.3. Geochemistry Dans les tudes gochimiques, il est souvent ncessaire de la que concentration 14 connatre 2C aN=14 [0.975 / (1 0.0225)] =0.4213 lanne initiale dun chantillon correspondant lanne dchantillonnage t14 ia(telle 14ou une 11.5.4.3 G EOCHIMIE Dans les tudes gochimiques, il est souvent ncessaire de connatre la concentration C a corrige pour lge et normalise, En utilisant la valeur In geochemical studies it is often necessary (telle que lanne ou une initiale dun chantillon correspondant lanne dchantillonnage t i or=42.13% [cf. 11.40]calcule ci-dessu cerne darbre sest forme), 14au lieu de lactivit en 1950, obtenue en routine. Comme la 14 to know theoriginal C content asample in lanne ou une initiale dun chantillon lanne dchantillonnage ti (telle conventionnel est: 14 correspondant cerne darbre sest forme), lieu de of lactivit en valide 1950, obtenue en routine. Comme la 14 Dans les tudes gochimiques, ilau est souvent ncessaire de connatre laque concentration C tre C (activit ou concentration) est pour lanne1950, elle doit concentration en a value calUsing thenormalised, age corrected theyear of thesample origin t (such as theyear 14 i cerne darbre sest forme), au lieu de lactivit en 1950, obtenue en routine. Comme la 14 C (activit ou concentration) est valide pour lanne1950, elle doit tre concentration en (telle que lanne ou une initiale dun chantillon correspondant lanne dchantillonnage t i culated above, theconventional C age is: et 14 1950: corrige pour14 la dcroissance radioactive lanne in dorigine (ti)ln atreering was formed), instead ofentre theactivity T = 8033 aN =elle 6943 BP tre Cdcroissance (activitau oulieu concentration) est pour lanne1950, doit concentration en et routine. 1950: corrige pour la radioactive entre lanne dorigine (ti) cerne darbre sest de lactivit envalide 1950, obtenue en Comme la 1950, as forme), is routinely obtained. As themeasured 14 14 i 14 la dcroissance a =6943 BP [cf. 11.50] T = 8033 ln ) et 1950: corrige pour radioactive entre lanne dorigine ( t i ( t 1950 ) / 8267 14 14 0 N content (activity valid for pour lanne1950, elle doit (11.46) i or concentration) is C= (activit est valide tre concentrationCen A A e ou Lactivit relative normalise est: 14 i 14 0 ( ti 1950 ) / 8267 theyear to be corrected for radioacA 1950, = A itehas (11.46) is: Thenormalised relative activity corrige pour la dcroissance radioactive entre lanne dorigine ( ti) et 1950: ( ti 1950 ) / 8267 of origin (t ) to 1950: 14 i decay 14 0 tive from theyear A = A e (11.46) i 14 et de la mme faon pour les valeurs normalises: N 14 =14 aN14 a1 = 1= 0,5787 or 578,7 = 0.5787 or 578.7 14 i 14 0 ( ti 1950 ) / 8267 N N et de la mme normalises: A = faon A epour les valeurs (11.46) (11.46) [cf. 11.42] et de la mme faon ( ti 1950normalises: ) / 8267 14 ipour 14les 0 valeurs A = A e (11.47) En supposant que les cernes sont dats, par dendrochronologie 5735 calBC ("ca N ( t 1950 ) / 8267 values: and equally thenormalised 14 iN 14 0 i Suppose thetreering 14 is dated dendrochronoANpour = for A (11.47) et de la mme faon les valeurs normalises: N e C, reprsente sur la Fig. 8.5), i.e. ti = = corrig selon la courbe de calibration ( ti 1950 ) / 8267 14 i 14 0 logically to 5735 calBC (stands for calibrated AN = AN e (11.47) (11.47) 14 14 Pour cette correction on doit de nouveau utiliser la priode C correcte (5730a) avec C calibration 14 BC=corrected according toconcentration the ( ti 1950 ) / 8267 14 i 0 la concentration corrige pour lge, i.e. avec la 14 A = 14 AN e on (11.47) Pour cette correction doit nouveau utiliser la priode (5730a) 5735 a. C originelle de lc N 1 14 0 de 14 0 14 C i correcte 14 i = curve, shown in Fig.8.5), i.e. t . Par ailleurs, again A et thecorrect a se rapportent 1950 et A et a lanne doriginei du = 1/8267a For this correction half-life of 14 alors: 1 4 0nouveau 14 0 utiliser Pour=cette correction on doit 1de la priode C14correcte avec du 14 1 . Par ailleurs, A et a se rapportent 1950 et Ai et 14ai (5730a) lanne dorigine 1/8267a C (5730a) has to be used with =1/8267a . carbone Theage-corrected, i.e. theoriginal 14C content of 1 contenu dans 14lchantillon. 0 14 0 14 i 14 i i i 14 14 14 14 14 0 14 0 14 i .Furthermore, Par ailleurs, A a aserefer rapportent et AN et a lanne = 1/8267a A et and to 1950 and A = aN 1is =(5730a) adorigine Pour cette correction on doit de nouveau utiliser la1950 priode C correcte avec du 1950) / 8267] 1 carbone contenu dans lchantillon. N exp[(5735 thesample then: 14 i normalises Pour les valeurs et corriges pour lge nous pouvons maintenant crire: 1 1 4 0 14 0 14 i 14 i and a tolchantillon. theyear theorigin of thecarbon carbone contenu dans . Par ailleurs, A et of acorriges se rapportent 1950 et pouvons A= et amaintenant lanne du = 1/8267a 0,0674(5) or = dorigine +67,4(5) Pour les valeurs normalises et pour lge nous crire: containing sample material. 14 i 14 14 i = a 1= a exp[(5735 1950) N N N carbone dans lchantillon. Pour les contenu valeurs normalises et corriges pour lge nous pouvons maintenant crire: 14 i A / 8267] 1 = 0.0674(5) or=+67.4(5) 14 i 14 i For thenormalised and age corrected values we 14 i = a 1 = 1= 14 A 0 Pour les valeurs normalises et corriges pour lge nous pouvons maintenant crire: i i 14 14 can now [cf. 11.49] ARN 1 = write: = a 1 14= i 0 A 14 ARN 14 i 14 i = a 1 = 14 0 1 = 208 14A i RN A 14 i 208 = 14 a i 1 = 14 0 1 = 123 ARN 208

AiTechniques de Mesure 1= 14 0 ARN

14

208

INTRODUCTION

11.5.4.4. Enhanced 14C radioactivity In studies on theextent of radioactive contamination, for instance by 14C, theabsolute radioactivity of thesample is required. In such cases, theresult of theroutine 14C measurement, in casu the 14a value, has to be converted back to theabsolute value by:
14 A = 14a 13.56 (dpm/gC) = 14a 0.226 (Bq/gC) (11.50)

This value has to be corrected for radioactive decay, as themeasured value is valid for 1950 instead of theyear of sampling ts=1986:
14

AS = 14A0 exp[(1986 1950) / 8267] [cf. 11.51]

= 0.4880 Bq/gC 11.5.4.5.

14

C ages

Themeasured activity as such is valid for theyear 1950 (Eq.11.38), so it has to be corrected for radioactive decay from 1950 (t0) to theyear of sampling (ts). Moreover, theactivity in this case is not to be normalised. If thelaboratory provides only normalised values, 14aN, these have to be de-normalised (i.e. normalisation removed) by applying Eqs.11.34, 11.38, 11.40 and 11.50: .

In geological and archaeological dating, theages used are theconventional 14C ages. is repeated. By international convention, the definition of theconventional 14C age is based on (Sect.8.1.4): (1) the initial 14C activity (i.e. theactivity of thesample material during growth equals thestandard activity in AD1950; (2) the 14C activities have to be normalised for fractionation (samples to 13=25, Ox1 to 19, Ox2 to 25) (see Chapter 10); (3) theoriginal (Libby) half-life of 5568 has to be used.

. . .

Theages are then calculated by applying: Conventional age=8033 ln14aN (11.52) This defines the14C time scale in years BP (Before Present, i.e. AD1950). This time scale needs to be calibrated in order to obtain historical (calibrated) ages (calAD, calBC, calBP). For thecalibration procedures and conventions we refer to thespecial Calibration Issues, published by Radiocarbon (themost recent edited by [81]). 11.5.5. Summary Theinterrelation between thevarious definitions and symbols, especially concerning thevalidity over thetime scale from past to present, is illustrated by Fig.11.9. For comparison, thesymbols used by [76] are given within brackets. In Table11.5 all symbols used for reporting 14C data are classified. Table11.6 contains therelative and absolute 14C contents of theavailable 14C reference samples. Therational symbols introduced by [77] are based on:
14

. (11.51) . 14 0 where t0 and a both refer to theyear 1950, and ts and AS to theyear of sampling; is based on thetrue 14C half-life of 5730 year; 14aN is theroutinely acquired (i.e. normalised) 14C content of thesample. Example: fall-out contamination TheAMS measured 14C concentration ratio is:
14

aN=2.200 or=220.0%

The 13 analysis obtained in theAMS system resulted in:

13

=32.0

Theroutinely obtained 14aN value now has to be de-normalised according to: a=14aN [(0.968/ 0.975]2=2.168(5) or=216.8(5) % [cf. 11.40]
14

Theabsolute activity in theyear 1950 would have been:

14

A0 = 14a0 0.226 = 14a 0.2260 = 0.4901 Bq/gC [cf. 11.50]

124

A = absolute radioactivity (in Bq/gC or in dpm/gC)

measuring techniques

14

Ai a

14

A0

14

AS

14 i 14 i

14 0

a = 14a = 14 ( d14C)
14 S

( 14C)

14 0

past
14

AD 1950
14 14 0 A0 A RN N and

present
14

future

A iN a iN iN ( )

AS N aS N
14 S N ( C)

14 14

14 14

a0 N = 0 N =

14 14

aN

14 14

N ( D14C)

Fig. 11.9. Illustration of thedefinition of symbols for reporting 14C data along thetime scale from thepast (for the data to be corrected for age/decay), via the year 1950 to the time of sample collection (s) and the future. Above theline are thenon-normalised data (not corrected for isotope fractionation), below thenormalised values. Thebold symbols are defined in this paper, thesymbols within brackets were defined by [76].

TABLE 10.5. Review of thesymbols used in reporting 14C activities.

measured at t0 (1950); aand at any time
14

normalised AN

Absolute 14 C content of sample Absolute 14 C content of standard 14 C abundance ratio Relative 14 C content

decay corrected till sampling at ts

14

decay corrected + normalised

14

age corrected from origin at ti

14

age corrected + normalised

14 i A N

A0

14

AS

AS N

Ai

AS

ASN
14

ARN AABS
14 S

AON
14

a= a

14 0

14

aN

14 S N

a a

14 i

14 i N

a a

AS/AON
14

ASN/AON
14

AS/AABS
14 S

ASN/AABS
14 S N 14 i b

= 140 d C
14

14 i N c

D C
14

C
14

C
14

C
14

Note: Theupper symbol is defined in this paper. Thesymbols in theshaded areas refer to [76]. In the3rd column thesymbols apply to thedecay-corrected values, i.e. corrected for decay of thesample activity from 1950 to theyear of sampling (Eqs.11.4344). Thesymbols in the6th column refer to Eqs. 11.4749. Thesuperscript 0 assigns thevalue to theyear 1950. Symbols stand for: A= absolute activity or concentration a= activity/concentration ratio to standard = relative 14C content (i.e. deviation of activity or concentration from standard Super- and subscripts stand for: N=normalised 0=time zero AD1950 i=initial time of growth/formation s=time of sampling

1 2

Thesymbols proposed by [76] are shown in theshaded areas. They refer to thefollowing fields of study:

in hydrology theuse of the14a value (or rather 14aS) is more common in oceanography and atmospheric studies 3 in geochemical studies if age correction is possible 4 idem, such as past 14C variations from treerings.

125

INTRODUCTION

14

a=activity or concentration ratio between sample and standard (in %) =relative difference in activity or concentration (in )

14

Thesymbols are prefixing thesuperscript 14 like in theisotopic symbol 14C. Thesuperscripts i, 0, and S indicate thetime to which A, a, or are related. Thesubscript N indicates whether theactivities and concentrations are normalised.

TABLE 10.6. 14C content and 13 values of anumber of standards and secondary reference samples, available for distribution.
Type of material C1 C2 C3 C4 C5 C6 Ox1 Ox2 Marine carbonate milled Carrara Marble Freshwater carbonate travertine deposit Cellulose from 40-yr trees felled 1989 Subfossil wood from peat bogs N.Zealand Subfossil wood buried bed forest USA Sucrose originally second. standard Oxalic acid primary 14C standard nr.1 Oxalic acid primary 14C standard nr.2
14

aN (%)

13

() +2.42 8.25

14

A0 (Bq/gC) N

distributed by IAEA IAEA IAEA / CIO IAEA / ANU IAEA IAEA / ANU NIST / IAEA NIST/ IAEA

0.00 0.02 41.14 0.03 129.41 0.06 0.32 0.06 23.05 0.02 150.61 0.11 100.00 a 127.36 0.04

< 0.0001 0.0930 0.2925 0.00072 0.05209 0.3404 0.2260 0.2878

24.91 23.96 25.49 10.40 19.20 17.60

by definition

Note: Thetypes of material and theages represent therange of interest of theradiocarbon laboratories. Thevalues are normalised for their 13 value (to 25). As the14C values presented by 14a (Eq.11.36), thetime of measurement is irrelevant. Absolute activities are calculated according to Sect.11.5.4.4, and refer to theyear 1950. Full details are reported by [115] NIST=National Institute of Standards and Technology, Atmospheric Chemistry Group, B364, Building 222, Gaithersburg, MD 20899, United States of America IAEA=International Atomic Energy Agency, Analytical Quality Control Services, Agencys Laboratory, Seibersdorf, P.O. Box 100, A1400 Vienna, Austria, fax +431206028222 CIO=Centre for Isotope Research, Nijenborgh 4, 9747 AG Groningen, theNetherlands, tel. +31503634760, fax +31503634738

126

12. natural isotopes of elements other than h, c, o

In this chapter we are dealing with theless common applications of natural isotopes. Our discussions will be restricted to their origin and isotopic abundances and themain characteristics. Only brief indications are given about possible applications. More details are presented in theother volumes of this series. Afew isotopes are mentioned only briefly, as they are of little relevance to water studies. Based on their half-life, theisotopes concerned can be subdivided: (1) stable isotopes of some elements (He, Li, B, N, S, Cl), of which theabundance variations point to certain geochemical and hydrogeological processes, and which can be applied as tracers in thehydrological systems; (2) radioactive isotopes with half-lives exceeding theage of theuniverse (232Th, 235U, 238U); (3) radioactive isotopes with shorter half-lives, mainly daughter nuclides of theprevious catagory of isotopes; (4) radioactive isotopes with shorter half-lives that are of cosmogenic origin, i.e. that are being produced in theatmosphere by interactions of cosmic radiation particles with atmospheric molecules (7Be, 10Be, 26Al, 32Si, 36 Cl, 36Ar, 39Ar, 81Kr, 85Kr, 129I) [116]. Theisotopes can also be distinguished by their chemical characteristics: (1) theisotopes of noble gases (He, Ar, Kr) play an important role, because of their solubility in water and because of their chemically inert and thus conservative character. Table 12.1gives thesolubility values in water [117];. Thetable also contains theatmospheric concentrations ([118]: error in his Eq.4, where Ti/(T1) should read (Ti/T1); (2) another category consists of theisotopes of elements that are only slightly soluble and have very low concentrations in water under moderate conditions (Be, Al). These are primarily used for sediment studies and for dating ice sheets; (3) two elements (N, S) have isotopic abundances revealing information on bio(geo)chemical processes in soils and associated waters; (4) three nuclides are cosmogenically produced isotopes from elements that occur as solutes in aqueous systems (Si, Cl, I) and are used for water dating; (5) thedecay series of uranium and thorium contain several isotopes of which therelations between theparent/daughter activities are useful pre-eminently.

TABLE 11.1. Solubilities of noble gases in water at various temperatures, theatmospheric concentrations and theconcentration of thenoble gases dissolved in water in equilibrium with theatmosphere at 10C [117, 118].
Solubility in mL (STP)/L H2O 0C Helium Neon Argon Krypton Xenon Radon 9.53 12.6 53.5 111.2 226 510 10C 9.07 11.4 41.7 81.2 154 20C 8.82 10.5 34.1 62.8 112.5 30C 8.74 10.0 29.0 50.9 86.7 Atmosph. concentr. 5.24 106 1.82 105 9.34 103 1.14 106 8.60 108 Diss. conc. mL/L (10C) 4.75 105 2.07 104 3.89 101 9.26 105 1.32 105

127

INTRODUCTION

In thetables at theintroduction of each section some relevant physical information is given about abundance and decay to finally astable daughter nuclide. This chapter mainly serves to review thephysical and chemical characteristics of theisotopes. Only abrief indication is being given of thepossibilities of application for studying thewater cycle. Athorough discussion is to be found in theother volumes of this series. 12.1. Helium Table 12.2. Natural isotopes of helium.
3 2

12.1.2. Experimental and technical aspects In groundwater concentrations of helium are observed in therange of 105 to 102mL(STP) of He/mL of water. With 3He/4He ratios of 108 to 107 this means that the3He concentrations can be as low as 1013mL/mL of water. To measure these amounts of gas, specialised mass spectrometers are needed. This is even more true for themeasurement of extremely low 3H contents (down to 102 TU) through 3He accumulation (Sect.12.1.5.2). In general, water samples are collected of 5 to 500mL depending on thelaboratorys equipment- and thoroughly sealed before being shipped to thelaboratory. 12.1.3. Sources of 3He Themain complication is that theprinciple of H/3He dating is based on theassumption that all 3He in thewater sample is tritiogenic (coming from decay of 3H). However, part of the3He may be of terrigenic origin (from in situ production according to Eq.12.2), part from theoriginal equilibration of thewater with theatmospheric gases. Thelatter contribution can be estimated from theNe concentration, which can not be of terrigenic origin. Apossible terrigenic contribution is to be estimated from theconcentration of 4 He (also corrected for theatmospheric component [29]. These processes are summarised by:
3 3

He

4 2

He

Stability Natural abundance fraction Natural abundance in air a Natural abundance in groundwater b
a b

Stable 1,3 10
6

Stable 100% 5,2 106 103 105

6,8 1012 1010 1013

mL gaz /mL of air mL gaz /mL of water

12.1.1. Origin and characteristics Theradioactive isotope of hydrogen, formed in theatmosphere by anuclear reaction of nitrogen atoms with neutrons in cosmic radiation (Sect.8.3), decays through decay to 3He:
3

H He +
3

(12.1)
4

Hetot = 3Heatm + 3Heterr + 3Hetrit Hetot = 4Heatm + 4Heterr

(12.3a) (12.3b) (12.3c)

The maximum energy of 3H is 18 keV and thehalf-life is 12.43 a(Fig.8.2). Thedaughter product 3He is stable and chemically inert. 3He is also formed in theearths crust (primarily in crystal rock) by thereaction:
6

Netot = Neatm where theatmospheric Heatm/Neatm=0.288.

concentration

ratio

Li + n 3He + 4He or

Li (n, ) 3He

(12.2)

Theunderground neutrons originate from spontaneous fission of uranium or thorium isotopes or by ( ,n) reactions in which theparticles are from decays within theuranium and thorium decay series.
4 235

12.1.4. Natural abundance The3He/4He ratio in atmospheric helium is about 1.3106, with ahelium concentration of about 5 ppmv (partial pressure of 5106 atm.). Therelative constancy of this concentration is due to thestate of equilibrium between theloss of helium from thecrust to theatmosphere and theloss from theatmosphere to outer space.

He originates primarily from thenatural decay of U, 238U and 232Th in theearth (Sect.12.13).

128

natural isotopes of elements other than h, c, o

Groundwater concentrations are observed of 103 to 105mL(STP)/mL of water, far exceeding theequilibrium value due to relatively high underground helium production. The3He/4He ratio in groundwater is still within anarrow range of 5108 to 107. Apart from the infiltration of tritium containing water, 3H can be produced underground in theaquifer, i.e. through in situ production:
14

12.1.5.2. Mass spectrometric measurement of 3 H through 3He Very low 3H abundances (theoretically down to 0.0005 TU) can be measured by thoroughly degassing and storing 50 to 100mL of water sample for at least half ayear in atightly sealed container and subsequently recollecting thedecay product of tritium, 3He. Theamount of this inert gas can be quantitatively measured mass spectrometrically. The3He produced during this storage time (t) is (Eq.12.5):
3

N + n 12C + 3H

(12.4)

Thepresence of neutrons is due to spontaneous fission of U and Th. Because of its short halflife, 3H levels will be low, generally below 1 TU. Theaccumulated 3He levels will then depend on thedegree of isolation of thewater, and are thus ameasure of that effect. 12.1.5. Applications 12.1.5.1. Principle of 3H/3He dating Theapplication of 3H to obtain underground residence times (ages) of groundwater was shown to depend on our knowledge of the3H input from atmospheric precipitation (Sect.8.4.2). Studying therelation between 3H and 3He offers thepossibility to determine ages without knowing thetritium input function. If theoriginal 3H content of theinfiltrating precipitation is 3H0, thecontent after aresidence time t, 3Ht, is presented by:
3

Het = 3H0 3Ht = 3H0(1 et)

so that theoriginal 3H content of thesample was:

3

H0 = 3He/(1 et)

(12.7)

To give an impression: theamount of 3He formed during half ayear storage of 100mL of water with a3H concentration of 0.5 TU is:
3

Het = 0.51018 2 (100/18)

(1 e(ln2)/12.43) 0,5) 22.41103 = 3.41015 mL 12.2. Lithium TABLE 12.3. Natural isotopes of lithium
6 Li 3 7 Li 3

Stability Natural abundance fraction

Stable 7.5%

Stable 92.5%

Ht = 3H0 et
3

Theamount of He formed during this time is equal to theamount of 3H lost by decay:

3

12.2.1. Natural abundance In seawater theLi+ concentration is about 0.18mg/L. Theisotopic composition varies by about 10. 12.2.2. Experimental and technical aspects Natural variations in the6Li/7Li ratio may be related to areference sample, available from theIAEA and NIST, referred to as L-SVEC. With respect to L-SVEC, theLi isotopic composition of Li in seawater (6Li=(6Li/7Li) - 1) is 32. 129

Het = 3H0 3Ht = 3Ht(et 1)

(12.5)

The3H/3He age is then: t = (12.43/ln2) ln[3He/3H + 1] (12.6)

Most applications are related to shallow, young groundwater, using thebomb peak of 3H in theprecipitation during theearly 1960s. Theoccurrence of 3H and 3He at great depth may be due to fractures, cracks or leaking boreholes, or to in situ production.

INTRODUCTION

12.2.3. Applications The 6Li/7Li ratio has been used to study brines and their origin as evaporated (palaeo)seawater. Li isotopes are also being applied to crystalline rocks. 12.3. Beryllium TABLE 12.4. Natural isotopes of beryllium
Stability Natural abundance fraction Abundance in air/ice/marine sediment Half-life (T1/2) Decay constant () Decay mode / Daughter Be radioactive
7 4 9 Be 4 stable

ratio of (2.68 0.14) 1011. Be targets are prepared by mixing BeO and Ag. 12.3.3. Natural abundance Theatmospheric production rate (flux) of 10Be is about 300 atoms m2s1. This production rate varies with latitude, altitude and geologic times. It is (together with 27Al) rapidly washed out from theatmosphere by precipitation, and is subsequently incorporated in continental and marine sediments. 10Be concentrations are observed of (5 to 20) 108 atoms/g of sediment. In Antarctic ice concentrations have been observed of 107 atoms 10Be/kg of ice [119]. Theconcentration in, for instance, thesurface water of theocean largely depends on theresidence time of 10Be in thesurface layers. Values have been observed of about 7.5 105 atoms/L of water [120], with Be concentrations of 5 pM/kg (at thesurface) to 30 pM/kg of seawater (at depth) (pM=picomol=1012mol). 12.3.4. Applications Be is being applied in particular for dating marine sediments by studying theradioactive decay in thesediment core. Theespecially useful method of measuring both 10Be and 26Al is mentioned in Sect.12.6.4. With respect to thewater cycle is 10 Be being used for dating ice.
10

Be radioactive
10 4

100% ~5 mBq/m3 air 53.3 d 1.51107 s1 EC / 7Li 107 10 atoms/kg 1.5 106 a 1.51014 s1 - / 10B

12.3.1. Origin and characteristics Theorigin is cosmogenic, i.e. 10Be (together with short-lived 7Be) is continuously being produced in theatmosphere by theaction of thehigh-energy proton component in cosmic radiation, causing spallation of atmospheric oxygen and nitrogen atoms.
10

Be decays according to: (12.8)

Be + e 7Li

12.4. Boron 12.4.1. Natural abundance In themarine environment theelement boron is 3 primarily found as dissolved borate (BO 3 ). An important geochemical characteristic is theeasy incorporation of B in marine clays during Table 12.5. Natural isotopes of boron
10 5

Be 10B + (Emax = 560 keV, no radiation ) (12.9)

10

12.3.2. Experimental and technical aspects Although in principle theradioactive decay of Be can be measured, the specific activity is so low that this method is not applicable. Detection has become possible by theintroduction of theultrasensitive mass spectrometers (AMS). Therefore, 10Be is only being applied since the1970s. As usual, 10Be concentrations are compared with (related to) areference material, SRM 4325, available from theNIST, with a10Be/9Be
10

11 5

Stability Natural abundance fraction

stable 18.8%

stable 81.2%

which theboron isotopes are being fractionated [121].

130

natural isotopes of elements other than h, c, o

12.4.2. Experimental and technical aspects Measurement of theabundance ratio 10B/11B (0.23) is carried out by Inductively Coupled Plasma Mass Spectrometry [121]. 12.4.3. Applications Rare applications have been made in themarine system, related to boron isotope fractionation during adsorption processes of seawater and clay. The 10B/11B ratio of brines has been used in combination with 6Li/7Li to study therelation with old seawater. 12.5. Nitrogen Table 12.6. Natural isotopes of nitrogen
14 7

(1) nitrification, theoxidation from ammonia to nitrite and nitrate:

NO NO NH 4 2 3

(12.12)

(2) denitrification, thereduction of nitrate to molecular nitrogen:

NO NO ( NO ) N2O N2 3 2 (12.13)

(3) nitrogen fixation, theconversion of dissolved molecular nitrogen to organic compounds: N2 (aq) N-organic molecules (12.14) These processes are carried out by bacteria. Theresulting stable nitrogen isotope fractionation may be considerable, but is hard to predict. Generally, theisotopically light (14N containing) molecules are reacted more easily [122]. 12.5.3. Applications Strictly hydrological applications are not obvious. 15N primarily serves to study bio(geo)chemical processes in thehydrological environment. However, 15N in dissolved compounds can be applied to tracing water masses underground. 12.5.4.
18

15 7

Stability Natural abundance fraction

stable 99.63%

stable 0.37%

12.5.1. Experimental and technical aspects Themeasuring technique for nitrogen has been discussed in Sect. 11.2.2. About 2mg of N is needed for a15N/14N analysis (and if necessary thecombined 18O/16O analysis). 12.5.2. Natural abundance and isotope fractionation Theisotope ratio 15N/14N in thelargest nitrogen reservoir, atmospheric N2, is extremely constant, due to therelative inert character of nitrogen. Theatmospheric 15N/14N value is 0.0036765. Nearly all fractionation processes involving 15N in nature are kinetic. Only dissolution of N2 in water (equilibrium fractionation 15 N2(dissolved)/N2(gas) = + 0.85), and thediffusion of N2 are non-biological processes. Themajor + components in thenitrogen cycle are NH 4 and NO3. Fig.12.1 shows ranges of themost common N-containing compounds. Therelevant biochemical processes in thewater phase during which isotope fractionation occurs are:

O/16O in nitrate

Information on theorigin of nitrate is also obtained from theoxygen isotopic composition of thenitrate ion. It has been shown (quote by [123]; see also VolumeIV) that one atom is related to atmospheric O2 (18 ~ +20 relative to

Atmospheric N2 ,, Plant N Soil organics Sedimentary NO3 Natural gas N2 Soil NH 4 Soil NO3 Soil N2 Synthetic fertilizer Manure
GroundwaterNO 3

NO x

15

()

20

10

+10

+20

Fig. 12.1. Survey of 15 values of nitrogen containing compounds in nature. The15 values are given relative to theisotopic composition of air-N2.

131

INTRODUCTION

VSMOW-water). Theother two atoms are derived from theambient water (18 < 0 rel. to VSMOW-water). In synthetic fertilizers theoxygen is mainly coming from air-O2. Moreover, 18 appears to be nicely correlated with thedenitrification process. In conclusion, theoxygen isotopic composition is certainly avaluable tracer, although theinterpretations are not yet unique [124]. 12.6. Aluminium TABLE 12.7. Natural isotopes of aluminium
26 13

12.6.3. Natural abundance Theatmospheric production rate of 26Al is about m2s1. Theproduction rate, however, 1 atom varies with latitude, altitude and geologic times. This secular variation is parallel to that of 14C and 10 Be. 12.6.4. Applications Thenatural occurrence of 26Al is primarily being applied to dating ocean sediments. Theadvantage of aparallel use of 26Al and 10Be -actually theratio of thetwo activities- is that themethod then is not dependent of thevariations in production rate. From:
26

Al

27 13

Al

Stability Natural abundance fraction Natural abundance in sediment Half-life (T1/2) Decay constant () Decay mode / Daughter

radioactive

stable 100%

Al = 26Al0 e(Al)t and

10

Be = 10Be0 e(Be)t

~107 atoms/g quartz 7.16 105 a 3.071014 s1 +, EC / 26Mg

we calculate theratio: (26Al/10Be) = (26Al/10Be)0 et (12.18)

where = Al Be = 0,50 106 a1. Theratio decreases in time corresponding to this decay constant. Theother application is thedating of polar ice. 12.7. Silicon

12.6.1. Origin and characteristics Like 10Be, 26Al is being formed in theatmosphere by spallation of argon in theair induced by cosmic ray protons:
40

Table12.8. Natural isotopes of silicon

4 1 Si 28 29 14

Si

30 14

Si

31 14

Si

Stability Natural abundance fraction Natural abundance in rainwater Half-life (T1/2) Decay constant () Decay mode / Daughter

Stable Stable Stable 92.2% 4.7% 3.1%

Radioactive

Ar (p,sp) Al (12.15)
26 26

Theradioactive decay to branches:

26 26

Mg is through two (12.16) (12.17)

Al

26

Mg + (85%)
+ 26

5106 Bq/L 140 a 1.571010 s1 / 32P, / 32S

Al + e

Mg (15%)

shows thecharacteristic 511 keV line from annihilation of the+ particle. 12.6.2. Experimental and technical aspects Al is measured with AMS as Al2O3 containing less than 2mg of Al. This is mixed with silver powder for use as theaccelerator target.
26

12.7.1. Origin and characteristics Theorigin of 32Si is cosmogenic, i.e. it is being produced by bombardment of 40Ar atoms in theatmosphere by neutron from cosmic radiation:

132

natural isotopes of elements other than h, c, o

40

Ar (n,sp) 32Si (12.19)

It decays through - emission (Emax=100 keV) to theradioactive daughter 32P, which in turn decays through -emission to stable 32S with ahalflife of 14.3 d:
32 32 + 32

12.8. Sulphur Because theactivity of 32Si itself is hard to deter12.8 Studying sulphur in thewater cycle especially mine, because of theextremely low activity in na- SOUFRE concerns thebehaviour of dissolved sulphate. It is ture and thecomplicated decay process. TheconLtude du soufre dans le cycle de leau concerne principalement le comportement du often useful to study theoxygen isotopic composequence was that as recent as 1981 thehalf-life Il est souvent intressant dtudier la compositionin isotopique en oxygne des comp sition of thesulphate compounds, combination was still believed to be about 650 a. TheAMS 34 32 34 rapport 32 S/ S. combinaison avec le with S/ S. technique has allowed better (although still somewhat uncertain) measurements, resultingTableau in val-12.9. Isotopes naturels du soufre isotopes of Table12.9. Natural ues of 140 20 a. sulphur 12.7.2. Natural abundance
32 3
32 16

processus dissous (comprenant 32Si) avec la matrice du sol. Si + P + S (12.20)

groundwater. However, at present theabundance of 32 Si in groundwater is still problematic and 32Si dating is hardly applied. Thereason is primarily theocChapitre processes 12 currence of disturbing geochemical in thesoil, involving adsorption and exchange of dis32 solved silicate (including dans Si) with thesoil matrix. gochimiques perturbateurs le sol, impliquant lchange ou ladsor

Thecosmogenic Si activity is about 5mB/m of Natural abunStabilit Stable Stable Stable rainwater, again depending on latitude [125, 126]. 95.02% 0.75% 4.21% 0.02% dance fraction This value decreases more rapidly in thesoil, not Rpartition 95,02% 0,75% 4,21% because of radioactive decay but as aresult of ad- de labondance naturelle sorption to soil minerals. During theperiod of nu12.8.1. Experimental and technical clear weapons testing in theearly 1960s the32Si aspects activity was about 4 times as high, but thenatural 12.8.1 ASPECTS EXPERIMENTAL ET TECHNIQUE level has most probably returned. Variations in therelative abundance of thesul32 34 34 34 phur isotopes, S and are reported as 32 , S etdeS, sexpriment par Les variations dabondance relative des S, isotopes du soufre, fined as: 12.7.3. Experimental and technical aspects ( 34 S/ 32S) sample 34 = 1 (12.21) Theoriginal method of measuring a32Si activity is ( 34 S/ 32S) reference by chemically separating and purifying thesilicon As theinternationally adopted primary reference content of theoriginal sample and have theradioLa troilite du Canyon Diablo (TCD) a t choisie comme premire rfrenc 32 or standard has been chosen theCanyon Diablo active daughter P accumulating in this silicon for internationalement accepte, il sagit de la phase FeS dune mtorite mtallifre p Troilite (CDT), theFeS phase from an34 iron mesome months. This example of atransient equilib32 S/ S est de 0,045005. Ce Cratre Mtor, en Arizona et around dont le Meteor rapport absolu teorite collected Crater, Arizona rium between aparent and daughter activity was 34 il quelques avec ce matriau, a t dcid choisir un nouveau matriau with an absolute S/32S ratio ofde0.045005. treated in Sect.6.6.1. it was shown in Fig.6.5 that problmes 34 32 dfini afew relativement au CDT. Une procdure partir duquel le est since However, problems showed up with analogue ce themaximum daughter (in casu P) activity is this material, it wasa decided to establish anew stables du carbone et de loxygne t engage: le nouveau "standard", NZ1, une p reached in aperiod of afew daughter half-lives. reference material, of which 34 is carefully deThe 32P activity is relatively easy to detect apart dAg 2S, a t accept pour dfinir la nouvelle chelle V-CDT qui est trs proche de l fined relative to CDT. An analogous procedure from thevery low intensity- because of thesimple 34 was followed as for thestable decay scheme: only one decay with Emax of 1.7 (NZ1 vs / V-CDT) = 0,30 carbon and oxygen isotopes: thenew standard, NZ1, ahomoMeV, and no g radiation. Thechemical extraction geneous Ag2S powder, has been par accepted procedure is laborious since silicate is to be sepa- toutes Dsormais les valeurs de 34 sont donnes rapportto audeV-CDT (trs proche thenew V-CDT scale which is very close to rated from more than am3 of water or ice. De plus, une fine srie dchantillons de rfrence supplmentaires est en prparation sous theoriginal CDT scale: [127] applied theAMS technique to theanalysis de lAIEA. of 32Si. 34 (NZ1 vs / V-CDT) = 030 (12.22) 12.7.4. Applications

Stability

Stable

34 36 16S 16S 32 S 33 16 Stable SStable Stable 16 33 16

34 16 S

Furthermore, aseries ofde additional reference samOriginally 32Si was expected to close thegap composs initiaux tels que SO42 (dissous o prpar par oxydation de Ag 2S form 14 ples is in preparation thecare ofde theIAEA. in thedatable-age range between 3H and C inou des gazeux, sulfures solides. Unby inconvnient lutilisation de SF6 est que la
fluorine ncessite des prcautions de scurit extrmement strictes. 224

Des mesures de spectromtrie de masse sont ralises sur SO2 et SF6 gazeux. L niveau de SO la mesure du rapport du faisceau dions rela[66]/[64] = [34S16O2]/[3 34 2 est que From now on all values are given S18theoriginal O16O] dans leCDT. faisceau de masse <66 une correction cause de la prsence de [32 tive to V-CDT (very close to

133

INTRODUCTION

Mass spectrometric measurements are carried out on gaseous SO2 or SF6. Thedisadvantage of thefirst is that, measuring theion beam ratio [66]/ [64]=[34S16O2]/[32S16O2] acorrection is needed for thepresence of [32S18O16O] in themass<66> ion beam. SO2 is prepared by oxidation of Ag2S 2 made of original compounds such as SO 4 (dissolved or crystalline), gaseous H2S, or solid sulphides. Adisadvantage of theuse of SF6 is that handling fluorineneeds extremely strict safety precautions. For a34S/32S analysis about 100mg of S is needed, at thesame time sufficient for a18O/16O analysis of theoxygen content of sulphate. 12.8.2. Natural abundance Variations in thenatural abundance are caused by chemical and biological isotope fractionation processes in thesulphur cycle. Isotopic exchange between dissolved SO2 4 and HS (for S isotopes) 2 and between SO 4 and H2O are extremely slow processes and can under surface conditions not been observed. On theother hand, biological (bacterial) processes cause kinetic isotope fractionation. In general, 34 S is enriched in sulphate such as dissolved in theoceans- and depleted in sulphide. This effect is observed during sulphate reduction, where S6+ is reduced to S2-. Theisotope fractionation involved is:
34 34 2 ( SO2 4 HS ) = R(HS ) / (SO 4 ) = 22 (12.23) 34

environment theisotopes can often be used to identify their sources. Furthermore, 34S/32S occasionally in combination with 18O/16O is applied to observe special biochemical processes in surface- and groundwater [128, 129] 12.9. Chlorine 12.9.1. Radioactive 36Cl 12.9.1.1. Origin and characteristics Production in theatmosphere goes through theaction of cosmic protons or neutrons:
40 36

Ar (p,sp) 36Cl (12.24) Ar (n,p) 36Cl (12.25)

Thecosmic-ray produced 36Cl fall-out rate from theatmosphere is estimated to be 26 atoms m2 s1. Underground 36Cl is being formed near thesurface by theaction of thermal (=low-energy) neutrons or cosmic-ray muons:
35

Cl (n,) 36Cl and 39K (n or ,)36K (12.26)

or at large depth by:

35

Cl (n,) 36Cl (12.27)

This production rate largely depends on theconcentration of uranium and thorium in theaquifer rock or sediment. Thermonuclear tests, especially in theSouthern Pacific ocean, have temporarily produced large amounts of 36Cl by neutron activation of chloride:
35

Oceanic sulphate and theevaporative minerals derived thereof have 34 values of + 20. The18 2 is + 9.6. value of oceanic dissolved SO 4 Rainfall sulphate, originating from oxidation of (CH3)S(CH3), dimethylsulphide, aproduct from decomposition of marine plankton, has 34 values of about + 5. 12.8.3. Applications Ageneral problem with sulphur isotopes is that isotopic values of certain compounds may vary greatly, even if thecompounds that have in principle thesame type of origin. Despite that, many exchange processes between S (and O) containing compounds mutually, and between these and water is that in theaqueous 134

Cl (n,) 36Cl (12.28)

12.9.1.2. Experimental and technical aspects Although 36Cl is radioactive and decays through energetic - radiation (max ~700 keV), quantitative detection is difficult because of thevery low specific activity. Measurements of the 36Cl abundance in water have been carried out by liquid scintillation [130]. Most natural 36Cl levels, however, came within reach with theintroduction of theAMS technique [131]. Thedetection limit for the36Cl/Cl ratio is about 1015.

36

N = 3,2 107(sec/an) F / [P (100 E)/100] atomes/L

(Lehman et al., 1991). Avec F = 26 atomes m2 s1, on obtient, dans un climat tempr

(0,6 3) 106 atomes/L. Dans la plupart des eaux souterraines, les valeurs natural isotopes of elements other than h, c, o considrablement plus leves. Cela est d la production in situ, i.e. souterraine de 36

chlorine

Les essais nuclaires ont apport des quantits importantes de 36Cl dans les eaux de me 1 This resulted in 36Cl in 1960, les retomb oms m2s Table12.10. Natural isotopes of partie injectes dans la .stratosphre. Durant le concentrations dbut des annes

augmentes des valeurs dans la gamme de 104 atomes m2s1. Cela rsultait en des c
35 17

water in theorder of 7108 atoms/L.

Cl

36 17

Cl

36 37

17

36 meanwhile to its original natural Cl dans leauCl de lordre de 7 returned 108 atomes/L. Cl

Stability Natural abundance fraction Natural abundance in water Half-life (T1/2)

Stable 75.5%

Radioactif 1015 to 1013 4105 to 5108 atomes/L 3.01105 a

retourn sonbe niveau dorigine, contrairement au 14 Entre-temps, le 36Cl est Stable creased levels can thus used naturel to trace infiltrated niveaux temporairement levs peuvent ainsi tre utiliss pour tracer leau dinfiltratio soil moisture during recent decades. 24.5% cours des dernires dcades.

level, contrary to 14C and 3H. Thetemporarily in-

12.9.1.4

APPLICATIONS

12.9.1.4. Applications 12.9.1.4.1. Dating old water

12.9.1.4.1 Datation de long leau half-life, ancienne 36Cl is suitable to date Due to its Decay constant groundwater, i.e. water in excess of 50000 7.301014 s1 En raison de old sa longue priode, 36Cl est adapt pour dater les eaux souterraines ancien () years old. For deep-underground water there vieilles de plus de 50 000 ans. Pour 36 des eaux souterraines profondes, il y a deux source Decay mode / i.e. (i) thecosmogenic are two sources of Cl, 36 36 36 / Ar et (ii) la production so la source cosmognique, reprsente par 36 R0 le rapport Daughter Cl/Cl ratio 36RCl/Cl source, depicted by the 0 , and (ii) 36 par activation des neutrons, reprsente par le rapport R . se Le rapport actuel m theunderground production by neutron activation chantillons deaux est alors: by theratio 36Rse. Theactual ratio depicted of 35Cl, to be measured in thewater sample is then: About 10mg of chlorine is needed for an AMS 36 R = 36R0 et + 36Rse (1 et) analysis. It is concentrated from awater sample 36 R = 36R0 et + 36Rse (1 et) or leached from asediment and precipitated as contenant le terme de production donn dans lEq. 6.30. AgCl, which is brought on thetarget holder. containing theproduction term given in Eq.6.30.
A partir de cela, lge de leau est:

12.9.1.3. Abundance in nature

36

From this thewater age is:

t= 1 ln R 36 Rse 36 R0 36 Rse
36

(11.29) Under natural conditions, Cl/Cl concentration 36 ratios are observed of 1015 to 1013. With achloride concentration of [Cl] mg/L of water,36 this 36 7 1 / (3.2 10 )s en Rseanalysant has to be ob- 36Cl/Cl des roc where 7 =ln2 (3,2 10 )s1. Rse doit tre obtenu le rapport comes to aconcentration of 36Cl atoms of:o = ln2 /tained 36 by analysing the Cl/Cl ratio of thesource
36

N = (61023103/35,5)(36Cl/Cl)[Cl] atoms/L

rock.

which is in theorder of (104 to 106) 36Cl atoms / L of water per mg/L chloride concentration. In order to estimate therecharge rate of 36Cl (36N) in atoms per L of infiltrating water, theamount of precipitation (P in mm/a) and evaporation (E in %) have to be known [132]: N = 3,2107(sec/an) F / [P (100 E)/100] atoms/L
36

12.9.1.4.2. Infiltration of young water By observing therelatively high 36Cl content of undeep water from theera of nuclear weapons testing, ages of infiltrated water can be determined of up to afew decades, resulting in values for theinfiltration rate [131]. 12.9.2. Stable 35Cl and 37Cl 12.9.2.1. Natural abundance and applications Because thechlorine ion, Cl-, is very little reactive, theisotopic variations denoted by; = (37Cl/35Cl)sample / (37Cl/35Cl)seawater NaCl 1 (12.30)
37

With F=26 atoms m2 s1 this comes in amoderate climate to arange of (0.6 to 3) 106 atoms/L. In most groundwaters theobserved values are considerably larger. This is due to thein situ, i.e. underground production of 36Cl. Thenuclear tests produced large amounts of 36Cl in seawater, subsequently in part injected into thestratosphere. During theearly 1960s the36Cl fall-out increased to values in therange of 104 at-

are very small. Attempts have been made to apply chlorine isotopes to study thecharacteristics of brines [133] and thedegradation and distribution of Cl containing contaminants [134]. 135

12.9.2.1 ABONDANCE NATURELLE ET APPLICATIONS Cl STABLES Parce que lion chlore, Cl, est vraiment peu ractif, les variations isotopiques caractrises par;
= ( Cl/ Cl)sample / (37Cl/35Cl)seawater NaCl 1
INTRODUCTION

NCE NATURELLE ET APPLICATIONS 37 37 35

aspects M A (* M A + M B ) [35 + 18n]([37 + 18n] + 18) From hundred litres of water sample thenoPour un taux = dhydratation de n = 4, le facteur de fractionnement rsultant estafew de 0,9987; pour n = 2, (12.31) (12.31) * M A 37 (M A + M B ) [37 + 18n]([35 + 18n] + 18) ble gases are extracted and argon separated gas = 0,9972 (cf. Eggenkamp, 1994). chromatographically. Thesubsequent proportion39 ation de n = 4, le facteur de fractionnement rsultant est de 0,9987; pour n =al 2, counting of the Ar decay requires at least For ahydration rate of n =4 theresulting frac12.9.2.2 A SPECTS EXPERIMENTAL ET TECHNIQUE 2L of argon extracted from about 15m3 of water tionation factor is 0.9987; for n=2, 37=0.9972 nkamp, 1994). [135]. This degassing procedure is carried ouit in [133]. AgCl est prcipit partir dun chantillon deau en ajoutant AgNO3. Il est purifi et ragit avec CH3I thefield. 37 35

(12.30) Cl, est vraiment peu ractif, les variations isotopiques caractrises par; 40 39 sont vraiment faibles. Des tentatives ont t faites pour in appliquer les isotopes du chlore ltude des Ar (n,2n) Ar (12.36) Stable isotope fractionation involved Cl- dif37 35 /35Cl) / ( Cl/ Cl) 1 (12.30) sample seawater NaCl caractristiques des saumures (Eggenkamp, et de la dgradation et de la distribution des fusion through sediments is 1994) equals theratio Therespective decay modes are: the diffusion coefficients contaminantsof contenant du Cl (Van Warmerdam(Sect.3.5). et al., 1995). Since Des tentatives ont theCl t faitesions pourare appliquer les isotopes du chlore ltude des hydrated, i.e. coupled to water 37 Arles +e 37Cl (12.37) sdiments est gal au Le fractionnement isotopique impliqu dans la et diffusion de Cl travers aumures (Eggenkamp, 1994) et de la dgradation dethechlorine la distribution des molecules, thediffusion constant of rapport coefficients de 1995). diffusion 3.5). Puisque les ions Cl sont hydrats, i.e. coupls des ion through water is (Sect. determined by themasses t du Cl (Van des Warmerdam et al., in combination with theemission of X rays, and O molecules). For of thehydrated ions (with n H molcules deau, la constante de diffusion de lion chlore dans leau est dtermine par les masses 2 les sdiments est gal 39 au topique impliqu dans la diffusion Cl travers 39 amedium thediffusion of de molecule M A through des ions hydrats (avec n molcules H2O). Pour la diffusion de la molcule un milieu de ArM K + (12.38) A travers sont hydrats, i.e. coupls des s de diffusion (Sect. 3.5). Puisque les ions Cl 37 therare (* indicates isotope, i.e. of molecules M B (* indique lisotope rare, i.e. Cl), le facteur de fractionnement est de (Eq.3.34): molcules MB 37 with amaximum - energy of 565 keV. Cl, is (Eq.3.34): nstante de diffusion de thefractionation lion chlore dansfactor leau est dtermine par les masses c n molcules H2O). Pour la diffusion de la molcule MA travers un milieu de M [35 + 18n]([37 + 18n] + 18) 37 37 A (* M A + M B ) = = le facteur (12.31) ue lisotope rare, i.e. Cl), de fractionnement est de (Eq.3.34): 12.10.2. Experimental and technical

* M A (M A + M B )

[37 + 18n]([35 + 18n] + 18)

pour donner du mthylchlorure, CH3Cl. Ce gaz est adapt la mesure du rapport Cl/ Cl par SMIR normale. 12.9.2.2. Experimental and technical aspects artir dun chantillon deau en ajoutant AgNO3. Il est purifi et ragit avec CH 3I 12.10.3. Natural abundance 37 35Mean La rfrence pour les isotopes du chlore est le Standard Ocean Chloride (SMOC), car la AgCl is precipitated from thewater sample by lchlorure, CH3Cl. Ce gaz est adapt la mesure du rapport Cl/ Cl par SMIR 37 The of 39Ar in theatAgCl is purified AgNO composition adding isotopique en chlorure de leau de mer est trs and constante. Lenatural rapport specific Cl/35Cl activity de ce 3. Theresulting mosphere is about 2mBq/L of Ar and is rereacted with CH3I to methylchloride, CH3Cl. This standard est 0,324. 37 35 to be constant within 7% ([136], corCl/ Cl ratio by car ported gasest is suitable for measuring the isotopes du chlore le Standard Mean Ocean Chloride (SMOC), la 37 35 to about 0.5mBq/m3 of water. IRMS. e en chlorure de normal leau de mer est trs constante. Le rapport Cl/ Cl de responding ce Underground 39Ar is produced in thepresence 12.10 ARGON

EXPERIMENTAL ET TECHNIQUE

12.10.1

Lisotope radioactif courte dure de vie de lArgon, Ar, est cosmognique en tant que produit de du Th et de U: de l40Ar, et est produit dans le sol par les neutrons issus des fissions 12.10.4. Applications E ETspallation CARACTERISTIQUES

Thereference for chlorine isotopes is Standard Mean Ocean Chloride (SMOC), as theisotopic ORIGINE ET in CARACTERISTIQUES composition seawater chloride is very constant. The37Cl/35Cl ratio of this standard 37 is 0.324. 12.10. Argon

of neutron from spontaneous fission of Th and U (Eq. 12.3335). The 37Ar abundance is much smaller (Table12.11).

its half-life of 269 years, 39Ar is suitable courte dure de vie de lArgon, 37Ar, est cosmognique en tant que produit With de 228 and characteristics to fill the gap in dating range between 3H and est produit dans le12.10.1. sol par les Origin neutrons issus des fissions du Th et de U: Theshort-living radioactive isotope of Ar, 37Ar, is cosmogenic as aspallation product of 40Ar, and is being produced underground by neutrons from Th and U fission:
40

C. Theadvantage is that it is chemically inert. However, thesubsurface production of 39Ar makes it problematic. On theother hand, thepresence of 39Ar is being used to indicate theunderground production of radioisotopes.
14

Ca (n,) 37Ar (12.32)

together with thelong-living argon isotope, 39Ar:

38

Ar has been shown an excellent isotope for dating glacier ice [137].
39

Ar (n,) Ar (12.33)
39

Ar is applied in oceanography to study thelargescale mixing and circulation.

39

39 42

K (n,p) 39Ar (12.34) Ca (n,) Ar (12.35)

39

12.11. Krypton 12.11.1. Origin and characteristics Thelong-living krypton isotope 81Kr is produced in theatmosphere by cosmic-ray induced spall-

Thelatter is primarily produced in theatmosphere by thereaction: 136

natural isotopes of elements other than h, c, o

Table 12.11.Natural isotopes of argon.

36 18

Ar

37 18

Ar

8 1 Ar 38

39 18

Ar

40 18

Ar

Stability Natural abundance fraction Natural abundance in air Natural abundance in water Specific activity in air (Bq/L) Half-life (T1/2) Decay constant () Decay mode / Daughter

Stable 0.33% 3.15105

Radioactive

Stable 0.06% 5.9106

Radioactive 8.51016 8500 atoms/L 1.68105 269 a 8.171011 s1 / 39K

Stable 99.6% 9.34103

70 atoms/m3 310
7 to 9

35.1 d 2.31107 s1 EC / 37Cl

ation of stable krypton (primarily of 84Kr), and by neutron activation according to:
80

Kr (n,) 81Kr (12.39)

traps and agas chromatographic separation, with aproper counting gas in aproportional counter. Afew hundred litres of groundwater are needed for such 85Kr analysis [135, 139]. 12.11.3. Natural abundance Thenatural abundance of thenoble gas krypton in theatmosphere is 1.14106 ppmv. Theestimated pre-nuclear concentration ratio of 81Kr/Kr is 5.21013, or aspecific activity of 1.5mBq/L of krypton. Under natural conditions 85Kr was much less abundant, with a85Kr/Kr value of about 3 1018. However, due to theemission of this isotope as afission product by thenuclear industry (primarily reprocessing of plutonium as anuclear fuel), thepresent-day concentration ratio amounts to 1.51011. Thesolubility of krypton in water is 9.3105mL(STP)/L. This means that themaximum concentration of 81Kr is 1300 atoms /L of water. Thenatural cosmogenic production rate of 85Kr is extremely small, due to thesmall reaction cross sections. However, 85Kr is an abundant fission product of uranium and plutonium and is as such during stages of nuclear fuel handling released to theatmosphere. From avery low pre-nuclear level, theatmospheric content has steadily increased to a specific activity of about 1Bq/mL (STP) of krypton in 1990, equivalent to amaximum 85Kr activity of about 0.07 Bq/m3 of water. 137

Thesame reaction is responsible for theproduction during nuclear test explosions, with additionally:
82

Kr (n,2n) 81Kr (12.40)

and through fission of uranium. The 81Kr contribution from bomb testing is considerably smaller than thenatural atmospheric 81Kr content [138]. Theunderground production of 81Kr is negligibly small. Kr decays by electron capture and emitting 13.5 keV X rays according to:
81 81

Kr + e (K) 81Br (12.41)

12.11.2. Experimental and technical aspects Kr is detected by radiometry or by AMS. Theconsequence of thelow 81Kr activity compared to thepresent-day 85Kr activity is that it is no longer possible to measure theatmospheric 81 Kr content by radiometric means.
81

For a85Kr measurement about 20mL of krypton gas is needed, to be extracted from thewater sample. Kr on theother hand can be measured radiometrically as amixture of afew mL of krypton, condensed from theoriginal sample by various cold
85

INTRODUCTION

Table12.12. Natural isotopes of krypton

78 36

Kr

80 36

Kr

81 36

Kr

82 36

Kr

Stability Natural abundance fraction Natural abundance in air Natural abundance in water Half-life (T1/2) Decay constant () Decay mode / Daughter

Stable 0.354% 4.0109

Stable 2.27% 2.59108

Radioactive ~51013

Stable 11.56% 1.317107

1200 atoms/L 2.1 105 a 1.051013 s1 EC / 81Br

83 36

Kr

84 36

Kr

85 36

Kr

86 36

Kr

Stability Natural abundance fraction Natural abundance in air Specific activity in air Natural abundance in water Half-life (T1/2) Constante de dsintgration () Mode de dsintgration/Fille

Stable 11.55% 1.316107

Stable 56.90% 6.48107

Radioactive 1.81011 2.11017 1.1mBq/L * 2.5106 Bq/L 10.76 a 2.04109 s1 / 85Rb

Stable 17.37% 1.98107

* Valid for theyear 1990, steadily increasing by about 0.025mBq/L per year [140].

12.11.4. Applications Deep groundwater, isolated from theatmosphere more than 50 years ago, does not contain 85Kr. Consequently 81Kr with its large half-life is in principle an ideal tracer for dating water with (isolation) ages of 50 ka to 1Ma. Theproblem is thecomplicated experimental handling and measuring procedure. The first AMS attempts have been promising [138]. As mentioned before, thecosmogenic origin of Kr is negligibly small. Therefore, this isotope serves to recognise young groundwaters, and to study their infiltration and hydrodynamics in thesoil, especially in combination with 3H.
85

non. It has also been brought into theatmosphere as afission product of uranium by nuclear bomb testing and thenuclear industry. It decays according to:
129

I 129Xe + (Emax = 150 keV)

(12.42)

Table12.13. Natural isotopes of iodine

127 53

129 53

Stability Natural abundance fraction Natural abundance in water Half-life (T1/2) Decay constant () Decay mode / Daughter

stable 100%

radioactive ~1012 5104 atoms/L 15.7106 a 1.401015 s1 / 129Xe

12.12. Iodine 12.12.1. Origin and characteristics I is naturally produced in theatmosphere by acosmic-ray induced spallation reaction on xe129

138

natural isotopes of elements other than h, c, o

12.12.2. Experimental and technical aspects Nowadays by far thebest detection technique is AMS, using 1 to 3mg of AgI, prepared from iodine extracted from the sample and purified by ion exchange procedures [141]. The129I/I detection limit at present is in theorder of 1015. 12.12.3. Natural abundance Thenatural abundance ratio 129I/I is about 1012. This level has increased locally by orders of magnitude due to nuclear bomb testing and therelease of 129I as afission product by nuclear reactors and reprocessing plants. In off-coast ocean surface water the129I/I ratio is estimated to be 1010. 12.12.4. Applications Most applications are devoted to analysing thenuclear-era levels of 129I. Especially thehigh levels in rivers and coastal waters near nuclear industries are being used for tracing oceanic mixing processes and thevertical transport of continental water in theocean. 129I/I values are being observed of up to 109. In groundwater the I/I ratio is mainly determined by therecharge rate, therate of leaching from theaquifer rock, and theamount of in situ uranium fission. Thelatter complicates thedating of deep groundwater.
129

dance of themembers of thedecay series is given in Table12.15. In old, geochemically undisturbed rock theuranium and thorium containing minerals contain all parent and daughter nuclides in astate of equilibrium. This means that, depending on therelation between half-lives, all members of thedecay series are directly or indirectly in secular equilibrium with theparent nuclide, 238U, 235U, or 232Th. In themost abundant 238U, for instance, each 238U is accompanied with adecay from each daughter, granddaughter, and so on. This means that for each 238U decay, now and in thepast, 7more decays take place. Thetotal number of 238U decays is thus equal to theemission of 8 particles of He atoms. Theconsequence is that, form theamount of helium gas in aclosed-system rock, theage, i.e. thetime elapsed since therock matrix became closed, can be determined. Thecalculation is avariant of thedaughter accumulation case, treated in Sect.6.7. Theamount of helium in L(STP) per kg of rock produced in aperiod of time T in arock with an present-day specific 238U activity of 238A kg1 of rock is: V = 8 238A(eT 1) (22.4/61023) so that theage T of this rock is T = (1/)ln{[61023V/22.4]/[8238A] + 1} (12.43) This method is referred to as theU-He dating method. Thesame holds for theother decay series, for 232Th with (232 208)/4=6 He atoms per decay and for 235U (235 207)/4=7 He atoms per decay. 12.14. Theuranium series This decay series is shown as thelower series in Fig. 12.2. All physical parameters concerning theradioactive decay are given in Tables 12.1412.16. 12.14.1.
238 238 238

12.13. Decay series In Sect. 6.6 we discussed thethree radioactive decay series. Each chain consists of aparent nuclide which has ahalf-life larger than theage of the universe, a series of successive and decays, and finally astable isotope of Pb. Because themasses of thesuccessive daughters change only by 4 units and decay hardly changes themass, we can speak of theThorium series, or the4n series (232Th to 208Pb), theUranium series, or the4n+2 series (238U to 206Pb), and Actinium series, or the4n+3 series (235U to 207Pb). Thehypothetical 4n+1 series (possibly 237Np to 209Pb) no longer exists because of therelatively small half-life. Several nuclides show branching decay (either or -); themain decay mode is indicated in Fig.12.2, showing thethree decay series. Thephysical information on thedecay and abun-

U/234U

astate of secular equilibrium (i.e. N = 234234N) theabundance ratio of 234U/238U is inversely proportional to their decay constants or proportional to thehalf-lives = 5.48 105, 234 238 while theactivity ratio A/ A=1. Thesolubility of uranium in water depends on 2 + theoxidation state. TheU6+ state (as UO 2 ) is 139

In

INTRODUCTION

more soluble that thereduced state U4+ (as UO+ 2 ). 234 238 As U and U are having thesame solubility in water, one would expect theactivity ratio in dissolved uranium to be=1. However, this is generally not thecase, because 234U is preferentially leached from therock. As aconsequence of therecoil energy given to the234Th daughter during the238U decay (Sect.5.3), thebond between 234Th (and thesubsequent daughters 234Pa and 234U) and thecrystal matrix is broken, so that the234U atom is more free to enter thesolution than theremaining 238U atoms. Theactual 234U/238U ratio in thewater depends on several (geo)chemical conditions within theaquifer. Values of 2 to 3, and up to 10 have been observed. Theabsence of an equilibrium between theactivities is referred to as the 234U/238U disequilibrium. Thegrowth rate of this ratio in aclosed system can be used to study thehydrogeological and geochemical conditions and thetransport of groundwater masses [142].

cause under marine conditions thestarting conditions (no Th isotopes, constant 234U activity) are relatively simple. 12.14.3.
226

Ra and 222Rn

Through recoil during thedecay of 230Th, 226Ra can easily be leached from therock matrix. Radium is present in solution as thedivalent alkali-earth cation and behaves chemically like Ca2+ and Ba2+. In groundwater specific activities can be observed of up to 5 Bq/L. Thedaughter of 226Ra is 222Rn, aradioactive radon isotope with ahalf-life of 3.8 days. As anoble gas, 222Rn is not being absorbed by solids. Moreover, it is highly soluble in water, contrary to 226Ra. Consequently, 222Rn is likely to accumulate in groundwater. The specific activity can exceed that of its parent 226Ra by orders of magnitude. Because of its short half-life, 222Rn is indicative for young groundwaters. As radon can easily be removed from water, thein-growth of 222Rn in artificially recharged water can be used to estimate residence times. 12.14.4.
210

In seawater the234U/238U ratio is also larger than one, due to theeffluence of continental freshwater. Commonly values of about 1.4 are being observed. 12.14.2.
230

Th 234U dating

Pb

Therelation between theactivities of 234U and its daughter 230Th is an example of atransient equilibrium (Sect. 6.6.2). Because Th is extremely insoluble in water, natural waters contain uranium isotopes in theabsence of Th isotopes. This is thebasis for adating method of corals [80] and continental sediments like peat [143, 144], referred to as UTh disequilibrium dating. 234U is being taken up by theorganisms or sediment without theradioactive daughter 230Th. Thelatter grows into thesample with increasing age. Equations apply discussed in Sect.6.6. Especially thedating of corals has been very successful, be-

For thesake of completeness we mention theexistence of arelatively long-living member of theuranium series, theradioactive isotope of lead, 210Pb. For hydrological applications this nuclide has little relevance. However, it is extensively used for measuring theaccumulation rate of ice or sediments. As an inert gas 222Rn escapes from thesoil and subsequently decays in theatmosphere by way of short-living daughters to 210 Pb (Fig.12.2). After ashort residence time in theair it is deposited either by wet or dry precipitation together with snow (to form ice) or sediment in water. Thedeposition rate is in therange

Table12.14, Natural isotopes of uranium

234 92

235 92

238 92

Stability Natural abundance fraction Half-life (T1/2) Decay constant () Decay mode / Daughter

radioactive 0.0057% 2.47 105 a 8.8921014 s1 / 230Th (decay series 206 Pb)

radioactive 0.7200% 7.038 108 a 3.12081017 s1 / 231Th (decay series 207 Pb)

radioactive 99.2743% 4.468 109 a 4.91561018 s1 / 234Th (decay series 206 Pb)

140

natural isotopes of elements other than h, c, o

decay mode

228

Th
228

232

Th

Ac
228

224

minor
220

Ra

Ra

Rn
231

235

Pa
231

212

Po
212

216

Po

227

Th
227

Th

Bi
212

Ac

208

Pb
208

Pb

223

Ra
223

Tl
219

Fr
234

Rn
219

U
234

238

215

At
215

At
230

Pa
234

211

Po
211

Po
215

Th

Th

Bi
211

Bi
226

207

Pb
207

Pb

Ra

Tl
222

Rn

218

At
218

210

Po
210

214

Po
214

Po

Bi
210

Bi
214

half-life > 1 year

Pb

206

Pb
206

Pb
210

half-life < 1 year stable

Tl
206

Tl

Hg

Fig. 12.2. Thethorium, actinium and uranium decay series according to theChart of Nuclides (cf. Figs 2.2 and 6.3). Thefinal stable lead isotopes are represented by ablack box, thelong-living nuclides (T1/2 > one year) by ashaded box. Thepreferential decay modes of branching decay and theresulting decay chain are indicated by adouble arrow.

of 6 to 10mBq cm1 a1 [145]. In ice or in aqueous sediments it decays with ahalf-life of 22.26 a, and can be applied for determining ages up to about 100 years. 12.14.5. Experimental and technical aspects Originally theactivities were measured by spectrometry [146]. Afew micrograms of uranium is needed for providing apure metallic, electroplated uranium source for an detector. Themodern mass spectrometric technique (Thermal Ionisation Mass Spectrometry, TIMS) needs less sample and has alower detection limit, while theresults are more precise and obtained faster. Thecapital investment, however, is afactor of 10 larger.

The activity of radon isotopes is measured by proportional gas counting. Theactivity of 210Pb is measured indirectly by detecting theingrowth of 210Po in thepure Pb source by counting. Similarly is theactivity of 226Ra measured by ingrowth of 222Rn in thepure radium sample. 12.15. Theactinium series Theinformation on decay and abundance is shown in Table12.14 and Table12.16. Thedecay scheme is presented in Fig.12.2. This series start with the235U parent and goes through 7 decays and 4 decays to stable 207 Pb. It is theless abundant isotope of uranium. 141

INTRODUCTION

Theconcentration ratio has been internationally established as 238U/235U=137.88. Thedaughter element of 235U, protoactinium (231Pa), is equally insoluble in water as thorium. This means that in an aqueous environment theelement Pa is rapidly removed from thewater. Thesediment then contains unsupported Pa, i.e. without 235U, so that thedecay of 231Pa in thesample is indicative for theage of thesediment. In thenext section 230Th will turn out to have thesame characteristic [147]. 12.16. TheThorium series Physical data on thedecay and abundance are given in Fig.12.2 and in Tables 12.1516. Theabundance and theapplication of thelongliving member of the238U series, 230Th, thedaughter of 234U, has been discussed in Sect.12.14.2. Also thecombination of thegeochemically analogous Pa isotope, 231Pa, both being highly insoluble in water and therefore unsupportedly included in amarine sediment, was mentioned

earlier. Especially thecombination of thetwo isotopes is valuable, because thedecay rates are different. It can be shown that this information cancels theneed for knowing both specific activities at thetime of sedimentation. Thechange of theinitial ratio of thespecific activities in time is indicative for theage. Thecouple of parent nuclide 232Th and daughter Ra plays arole in studying water-rock interaction. Important is thechemical difference between Th and Ra, thefirst being much less soluble than thelatter. Activity ratios that are expected to be=1 under conditions of decay equilibrium, may be <1 if therock minerals have lost 228Ra after 232Th recoil or if thesediment is accumulating 228 Ra from its parent decay, and > 1 where uptake of 228Ra has taken place from thesurrounding water.
228

Direct hydrological applications of 232Th are unlikely, due to theextremely low solubility of thorium in water.

Table12.15. Natural isotopes of thorium

230 90

Th

232 90

Th

Stability Natural abundance fraction Half-life (T1/2) Decay constant () Decay mode / Daughter

radioactive 7.5 10 a
4

radioactive 100% 1.4010 1010 a 1.56781018 s1 / 228Ra (decay series)

2.931013 s1 / 226Ra (decay series)

142

natural isotopes of elements other than h, c, o

Table12.16. Nuclear data on thedecay and abundance of themember nuclides of theuranium, actinium and thorium decay series (data from [148].
Half-life
238 235 234 234 231 234 232

Decay (), (), ,()

Abundance 99.2743% 0.7200% 0.0057%

218

Half-life Po Po Po Po Po 3.05m 0.15 s 1.78ms 164 s 0.30 s 0.516 s 138.4 d 7.4m 19.7m 60.6m 2.15m 5.01 d 26.8m 10.64 h 36.1m 22.26 a stable stable stable 1.30m 3.05m 4.8m 4.2m 8.1m

Decay ,() () (), (), ,() (), (), no

Abundance

U U U

4.468109 a 7.038108 a 2.47105 a 1.175m 3.28104 a 24.10 d 1.40101010 a 25.52 h 8.0104 a 1.913 a 18.72 d 6.13 h 21.77 a 5.76 a 1.60103 a 3.66 d 11.44 d 21.8m 3.82 d 55.6 s 3.96 s 0.9m ~2 s 0.1ms

216 215

Pa

214 212 211

Pa Th Th Th Th

Po Po Bi Bi Bi

Th Th

100%

210

231 230

215 214 212 211

228 227 228 227

Bi Bi

Ac Ac Ra Ra Ra Fr

210 214 212 211 210

Pb Pb

228 226

Ra

Pb

224 223

Pb Pb Pb Pb Tl Tl Tl

208 207 206

52.3% 22.1% 24.1%

223 222 220 219

Rn Rn Rn At At At

210 208

219

207 206 206

218 215

Tl

Hg

Note: Thedecay of and is followed by one or more g emissions. Where thedecay is branching, theleast abundant decay mode is given in parenthesis; a= year, d=day, m=minute, s=second

143

13. errors, means and fits

This chapter contains achoise of essential information on theanalysis of measuring uncertainties, and thetreatment of large numbers of data. Starting with adiscussion on errors, we arrive at atechnique of judging theprobability of thetruth of afinal result. 13.1. Errors In dictionaries theword error is defined as thedifference between theapproximated value as theresult of an observation or measurement, or acalculation- and thetrue value. Theproblem is that in general we do not know thetrue value, as this is generally theresult of ameasurement or calculation. Therefore, we have to find away of estimating thereliability of our result. The name errors is not well specified as such. We thus have to become more specific about thedefinition. Errors can be classified as follows: (1) Blunders or mistakes in measurement or calculation are usually apparent as being far from expectations. They are to be dealt with by repeating themeasurement or calculation. (2) Systematic errors are more difficult to detect. They are reproducible discrepancies, often theresult of afailure in theinstrumentation or a consistent mathematical insufficiency. They are to be found (and corrected for!) by repeating theanalysis with different equipment or by recalculation (by acolleague or by different means). (3) Random errors are themost common type of errors. They are theresult of theunavoidably limited quality of our instrumentation. They can only be partly overcome by refining theinstrumentation or theanalytical method, and by repeating themeasurements (such as reading atemperature or pH) or extending theobservation time (for instance, of radioactivity). 13.2. Precision and accuracy 13.2.1. Definitions It is important to distinguish between precision of and accuracy. (1) Theprecision of aresult is ameasure of thereproducibility of an observation, of how well theresult can be determined, irrespective of how close theresult is to thetrue value. Theassociated error is better referred to as theuncertainty of aresult. (2) Theaccuracy is ameasure of thecorrectness of an observation, of how close theresult is to thetrue value. The two sets of definitions we have given are simply related. Precision is ameasure of thesize of random errors. If we are able to reduce random errors, for instance by better equipment or procedures, theprecision of themeasurement is better, theresult is more precise, and theanalysis is more reproducible. Increasing theprecision by reducing random errors is atask of each single laboratory. On theother hand, asystematic error directly effects theaccuracy of themeasurement; avoiding or eliminating systematic errors makes theresult more accurate and trustworthy. Increasing theaccuracy of aresult is often thegoal of international intercomparisons by a number of laboratories analysing thesame set of samples, and by routinely running standards. For studying and eventually reducing systematic errors it is important to dispose of data with small random errors, with relatively high precision. On theother hand, it is awaste to spend much effort on increasing theprecision, if thesystematic error is large. Fig.13.1 illustrates thedifference between precision and accuracy. 13.2.2. Significant figures and digits When reporting numbers it is acommon rule to indicate the uncertainty by the figures and digits of thenumber given. If adistance is given as 5000km, it is common sense to trust only theleftmost figure. However, if one is also certain about thenext figure (theleftmost 0), it is better to write 5.0103km. In general, it is preferable to write numbers in thescientific notation, i.e. an

INTRODUCTION

argument in decimal notation with anumber of digits, multiplied by apower of 10. Therightmost digit contains theuncertainty. As arule theprecision of the uncertainty (i.e. thedegree of certainty of theuncertainty) is not better than 10% of theuncertainty. For example, if theradioactivity of asample is determined as 13.56 Bq, it may go with an uncertainty of 13.56 0.12 or 13.560.08, but giving an additional digit in theuncertainty like 13.560.081 would exaggerate thecertainty of theuncertainty. Theuncertainty also determines thenumber of digits quoted. For instance, it is right to quote 13.560.12 Bq, but it is not consistent to write 13.5640.12 Bq. In computer calculations all digits are to be kept; rounding off is done only with the final result. Nevertheless, results written down in thecourse of amathematical calculation are to be given with thenumber of digits that can be justified. Theen-

tire calculation itself, however, is to be carried out without intermediate rounding off. 13.2.3. uncertainties There are two different types of uncertainties. (1) Instrumental uncertainties, due to fluctuations in theresult of any instrumental observation, whether it concerns measuring theoutdoor temperature or weighing your letter on aletter balance, or applying fancy equipment to measure time in thelaboratory. An estimate of thesize of theuncertainty can be obtained by an educated guess, or by repeating themeasurement and observe thedistribution of theresults. (2) Statistical uncertainties, due to thefact that certain processes even theoretically show fluctuations. Aproper example here is theprocess of radioactive decay. Even (non-

Fig. 13.1. Example to illustrate precision and accuracy, showing two series of results from 19measurements of thesame radioactivity. A. Thedata are imprecise but accurate, giving theproper average value of 13.56 Bq. Thegrey area refers to the1 confidence level; i.e. 68% of thedata should be within this range (example in Sect.13.5.2). B. Thedata are precise, but inaccurate probably because of asystematic error, as theaverage value is now 13.50 Bq, instead of thetrue value of 13.56 Bq.

146

Chapitre 13 errors, means and fits

(2) Les incertitudes statistiques, dues au fait que certains mme thoriquement existing) ideal equipment would observe processus, xi + Dx have been observed, is tain range xi and montrent des fluctuations. La dcroissance radioactive estreferred un exemple the fluctuation in the activity measurement, to as caractristique. thesample distribution. Themean or thestatistical spread in pas) theresults. In des value is: Mme un quipement idal (qui nexiste observerait fluctuations dans la mesure cases like these procedures exist to deterde lactivit, ou une dispersion statistique des rsultats . 1Dans de tels cas, des x = N i xi ( x) andN = Ni mine theuncertainty beyond doubt. (13.4) N i procdures existent pour dterminer lincertitude au-del du doute.

13.3

13.3. Instrumental uncertainties 13.3.1. Mean values

within one column, suggesting agood statistical certainty, but abad resolution; if Dx is made too The mean or average value of theresult of 13.3.1 VALEURS MOYENNES small theresolution is increased, but few data fall anumber of measurements is defined as thesum column and thereliability appears to La valeur moyenne rsultant dunby grand nombre of demeasuremesures est within dfinie one comme la somme des of theresults divided thenumber be small (scattering histogram). ments: rsultats divis par le nombre de mesures: Themore measurements have been carried out, 1 N x xi ( x1 + x2 + x3 + ... + x N ) / N (13.1) thebetter is theimpression of thedistribution of N N 1 i =1 data around acertain mean value. For an infinite x xi ( x1 + x2 + x3 + L + x N ) / N (13.1) i =1 N is N thenumber of measurements, i stands for number of results with random errors thesample theserial number of an arbitrary measurement and x ismesures, theparameter measured. We will often dune mesure quelconque et x le N est le nombre de i reprsente le nombre de sries omit N and i=1, and simply write Sxi. paramtre mesur. On ignore souvent N et i = 1, pour crire simplement xi. Thenumber of measurements is always limited. Le nombre However, de mesures est toujours limit. Cependant, si on peut augmenter ce nombre if we would be able to increase this linfini, on obtiendra meilleure valeur de up la moyenne, dfinie alors ainsi number toune infinity, we would end with abetter value of themean, then defined as 1 lim ( xi ) (13.2) (13.2) N N Themedian is now defined as thevalue of theset La mdiane maintenant dfinie comme valeur dun jeu de donnes en dessous de ofest data such that theresults of halfla themeasurements is smaller, half is larger thanmoiti themedian laquelle se situent la moiti des mesures, lautre tant plus leve que la mdiane. Dans value. For asymmetrical distribution themean le cas dune distribution symtrique la moyenne et la mdiane sont quivalentes. Nous and themedian values are equal. We will later use utiliserons un peu plus loin la dviation (cart) dun rsultat par rapport la moyenne (ou la thedeviations of asingle result from themean mdiane), (or x xi; par dfinition moyen des rsultats median), x x ; bylcart definition theaverage de- par rapport la valeur moyenne viation est gal zro : of theresults from themean value equals zero:
i

is chosen to be too large, nearly all data may be INCERTITUDES INSTRUMENTALES

If in making thehistogram Dx or theclass width

Fig. 13.2. Histogram (block-shaped), indicating (13.3)of measurement results the irregular distribution within a range of xi(x) i.e. between xi and xi + x around a mean value; the deviations from the mean value (x ) rather than theactual results are given along with the number of observations (y-axis) for values 13.3.2. Distribution of data 13.3.2 DISTRIBUTION DES DONNES within a certain range. The smooth curve illustrates theGaussian distribution, which is thehypothetical reResults of anumber of measurements can be preLes rsultats dun grand nombre de mesures peuvent tre sult prsents sous forme dun of an infinite number of measurements. It also repsented in ahistogram, agraph showing thenumhistogramme, graphe indiquant le nombre de fois (axe des y) resents que lestheprobability rsultats indiqus sur (P) of data around distribution ber of times (y-axis) certain results indicated themean value. Thedeviations from theaverage value laxe des x ont tthex-axis obtenus (Fig. 13.2). along were obtained (Fig.13.2). It is are given in terms of thestandard deviation ().

______ 11 N N 11 1 1 = (x x)x= xi =x x= x x x ix ( ) = x N xN x= 0 x=0 xii x = N i i N N i =1 N i =1 N N (13.3)

246

obvious that theprobability of obtaining results further removed from themost frequent result is less and less probable. Thehistogram (or block diagram) consisting of columns representing thenumber of times (Ni) results xi(Dx) within acer-

On top of thegraph theintegral or summed probabilities are shown: the probability of observing values between x + and x is 68%, between x + 2 and x 2 thechance is 95% and finally between x + 3 and x 3 99.7%.

147

bonne certitude statistique, mais une mauvaise rsolution; si x est choisi trop petit on augmentera la rsolution, mais peu de donnes tomberont dans la mme colonne et la fiabilit Si lorsquon construit lhistogramme, on donne x ou la largeur de la classe une taille trop sera faible (histogramme dispers). forte, Presque toutes les donnes peuvent se trouver sur une seule colonne, suggrant une INTRODUCTION Plus on aura de mesures, meilleure sera limpression de distribution des donnes autour dune bonne certitude statistique, mais une mauvaise rsolution; si x est choisi trop petit on certaine valeur moyenne. Pour un nombre infini de rsultats avec des erreurs alatoires la augmentera la rsolution, mais peu de donnes tomberont dans la mme colonne et la fiabilit distribution distribution des chantillons est reprsente par une distribution forme dethebetter cloche normale deviation, theprecision, thenarrower is represented by abell-shaped nor- en sera faible (histogramme dispers). mal or Gaussian in which theprobtheGaussian xi est: ou Gaussienne , sur laquelle ladistribution probabilit ,dobserver une valeur de y = yi x = curve. ability of observing avalue y=yi at x=x Plus on aura de mesures, meilleure seraof limpression de distribution des donnes autour dune i is: If we now consider thereal set of measurements, 2 certaine valeur moyenne. Pour un nombre infini de rsultats avec des erreurs alatoires la thestandard deviation of theset is: y f ( x ) 1 1 i i (13.5) exp (13.5) une distribution i = chantillons distribution P des est reprsente par en forme de cloche normale i i 2 1 2 (x x) 2 (13.8) ou Gaussienne, sur laquelle la probabilit dobserver une valeur de y = yi x =x est: ii N 1 yi is themeasured value of thedependent variable yi est la valeur mesure de la variable dpendante y, f(xi) est de y calcule la of N is inserted in 2 thevalue Thefact that N1 pour instead y, f( xi) is they value calculated for of la valeur 2 1 1 y i f ( xi ) 1 2, quexi lon dfinira thedenominator is (13.5) discussed in i, P exp variable xii,est i is de- de la thestandard dviation standard plus valeur de latheindependent variable dpendante i = x i = = ( xi x ) 2 standard texts y x later. 2 i of2 i N N ( N 1 ) on statistical analysis. Thenecessity can be apviation y , to be defined Themost prob que lon observera, le mode, correspond au pic de distribution, i loin. La valeur la plus probable preciated by considering theextreme case of only able value to be observed, themode, corresponds i.e. le haut de la courbe lisse. Pour les donnes avec des erreurs alatoires la distribution est 1 x 2 one Asingle can give i to thepeak of i.e. to thetop =measurement. =y lhistogramme mesure dethedistribution, la variable dpendante yla , f( xi)of est la valeur de calcule pour la yi est la valeur ( xmeasurement i x) x symtrique autour du sommet. La Fig. 13.2 montre courbe Gauss avec N ( N 1) thesmooth curve. For data with random errors deno idea on theprecision of themeasurement. N dviation standardTherefore, de yi, que thefraction lon dfinira plus valeur denombre lathedistribution variable dpendante xi, i est la issu dun limit de mesures. is symmetrical around thetop. may not be areal number. loin. La valeur la plus probable que lon observera, le mode , correspond au pic de distribution, Fig.13.2 shows theGaussian curve together with and is included Thepossibility of calculatingx thehistogram resulting from alimited number of i.e. le haut de la courbe lisse. Pour les donnes avec des erreurs la distribution est 13.3.3 DVIATION STANDARD inalatoires modern pocket calculators. symtrique measurements. autour du sommet. La Fig. 13.2 montre la courbe de Gauss avec lhistogramme In Fig. 13.2 various confidence levels are indiissu dun nombre limit de DONNES mesures. DES 13.3.3.1 PRCISION cated. Theprobability that arandom result of 13.3.3. Standard deviation x + and x is ameasurement lies between Il est vident que si les erreurs alatoires sont faibles, les valeurs de la dviation (xi x) sont 13.3.3 DVIATION STANDARD calculated to be 68%. This means that arepeated 13.3.3.1. Precision of data petites et la distribution des rsultats autour de la moyenne sera plus resserre.will La dviation measurement result in anew result within It is obvious that if random errors are small, moyenne est une mesure de ltendue des donnes autour de la moyenne, ce que lon appelle deviation is the68% of themean: thestandard 13.3.3.1 thevalues PRCISIONof DES DONNES (x thedeviation x ) are small and i confidence level, 2 simple is the95% confidence level, la dispersion du jeu de donnes. L Eq. 13.3 a montr que lon ne peut pas utiliser la thedistribution of theresults around themean is and 99.7% is the3 confidence x) sont level. Il est vident que si les erreurs alatoires sont faibles, les valeurs de la dviation ( x i moyenne de toutes les dviations,deviation une consquence de la narrower. Theaverage is ameasure of dfinition de la moyenne. La petites et des lathespread distribution rsultats autour de moyenne resserre. dviation moyenne valeurs absolues desaround dviations, i.e.la indpendamment de leur signe, La caractrise of des thedata themean or theso- sera plus moyenne est une mesure de ltendue des donnes autour de la moyenne, ce que lon called dispersion of thedata set. Eq. 13.3 has 13.3.3.2. Precision ofappelle themean mieux la dispersion : shown that we can not use thesimple average of la dispersion du jeu de donnes. L Eq. 13.3 a montr que lon In ne thepreceding peut pas utiliser la simplewe have been deal____ discussion all deviations, aconsequence of thedefinition of 1 moyenne ded toutes les une consquence de la dfinition la moyenne. ing with de theprecision of La data, as characterised xi dviations, x (13.6) themean. Theaverage of theabsolute values of N absolues moyenne des valeurs des dviations, i.e. indpendamment de leur signe, caractrise by thestandard deviation. It is equally important thedeviations, i.e. irrespective of their sign, charto report thepas uncertainty in the final outcome of mieux la dispersion :thedispersion Pour des raisons mathmatiques cependant, nest appropri. acterises better: utiliser les valeurs absolues anumber of measurements. Therefore, we have to Cest pourquoi, prend les carrs des dviations pour caractriser la distribution. La valeur ____ on1 calculate theprecision of themean value or, more 1 xi x (13.6) d x (13.6) ainsi obtenued est appele variance: N xla i specifically, thestandard deviation of themean. N For mathematical reasons however, using abBelow we will briefly discuss thepropagation of Pour des raisons mathmatiques cependant, absolues nest pas appropri. 1utiliser 1 appropriate. 2 2 les valeurs 2 solute values is not Therefore, errors; i.e. theoverall uncertainty obtained from lim ( xi ) = lim xi (13.7) N prend N Cest pourquoi, on carrs dviations pour caractriser la distribution. La valeur charac of les des N N thesquares thedeviations are taken to anumber results, each with its own uncertainty. 1 2 terise thedistribution. Theresulting value is re- ainsi obtenue est appele la variance: Theconclusion is that thevariance of amean is ( x x ) i 248 N 1 of thedata set divided by thenumber ferred to as thevariance: thevariance 1 ( xi x ) 2 measurements: of 1 1 2 2 2 N 1 lim ( xi ) = lim xi (13.7) xi 2 N N 1 2 N N = = ( xi x ) 2 (13.9) x 2 N ( N 1) N (13.7) 1 x 2 2 i 248 = x = ( xi x ) Thevariance is thus theaverage of thesquares N1 ( N 1)of themean xi N deviation Thestandard is then: = ( xi x ) 2 minus thesquare of theaverages. Thequantitative x = N (N 1 1) Nx measure of thesize of therandom errors, i.e. of x = i = ( xi x ) 2 (13.10) thestatistical spread of thedata around themean, N ( N 1) N or in other words of theprecision is now given As an example we will calculate themean by thestandard deviation , which is thesquare and standard deviations of thedata shown in root of thevariance. Thesmaller thestandard

Chapitre 13

148

errors, means and fits Chapitre 13

Erreurs, Moyennes et Ajustements Erreurs, Moyennes et Ajustements

A titre dexemple nous calculerons la moyenne et les dviations pour les donnes precision is betItstandards is obvious that therelative TABLE 12.1. Set of data 1 corresponding to Fig.13.1A. ter thehigher thecounting R indiques sur la Fig. 13.1A et le Tableau 13.1. On suppose que = 1 les donnes ont la rate and thelarger Rtoutes themeasuring time. = R Rt mme incertitude/prcision. No. xi Nr. xi R xi x xi x Rt The matter of confidence levels with observ1 11 13.55 0.01 13.51 0.05 ing data with statistical uncertainties Il est vident que la prcision relative est meilleureis sisimilar le taux de comptage es Il est vident que la prcision relative est meilleure si le taux comptage est 2 12 13.45 0.11 13.63 +0.07 to theinstrumental uncertainties as discussed inde lorsquon temps de mesure plus long. Le cas des niveaux de confiance obs Tableau 13.1. Jeu de donnes correspondant la Fig.13.1A. temps de mesure plus long. Le cas des niveaux de confiance theprevious section. Theprobability that atrue lorsquon obser 3 13 13.57 +0.01 13.52 0.04 avec les incertitudes statistiques est similaire celui des incertitudes instru value observed in anest infinite period of time avec les incertitudes statistiques similaire celui des lies incertitudes instrum 4 14 13.68 +0.12 13.55 0.01 en avons discut dans la partie prcdente. La probabilit pour quun nous between x + and x of themeasured value i i nous en avons discut dans la partie prcdente. La probabilit pour quune 5 15 13.63 13.45 0.11 is une 68%: thestandard deviation is the68% confi - et xi de l sur priode de temps infinie se situe entre x + x xi priode Nr. xi xi+0.07 xi observe xi x Nr. x Nr. x temps i observe sur une de infinie se situe entre xi i+ et xi de la dence level, 2 is the95% confidence level, and 6 16 13.47 0.09 13.62 +0.06 est de 68%: la dviation standard est le niveau de confiance 68%, 2 est de 68%: la dviation estlevel. le niveau de confiance 68%, 2 es 99.7% is the3standard confidence 13.55 13.45 1 8 +0.13 0.01 0.11 7 17 13.40 13.69 13.74 0.16 +0.18 15 95%, confiance et 99,7% correspond au niveau deconfiance confiance 3 confiance 95%, et 99,7% correspond au niveau de 3 ..
2 8 13.45 13.40 0.11 0.16 918 13.56 13.65 +0.00 +0.09 16
9 3 13.56 13.57 +0.00 +0.01 19 10 13.45 0.04 0.11 17 13.52 13.5

deviation 10 13.52 0.04 11 13.68 +0.12 13.51 13.65 Standard +0.09 4 18 13.5.1. 0.05 We often want to determine aquantity Athat is x =13.56 Note: 13.63 +0.07 13.63 +0.07 13.45 5 Mean 12 13.5.1 DVIATION STANDARD 0.11 13.5.1 19 afunction DVIATION STANDARD of one or more variables, each with Standard deviation x={(xi 13.56)}/18 =0.095 13.47 13.52 6 of 13 0.09 0.04 mean= its own uncertainty. Theuncertainty of each of dune On veut souvent dterminer une quantitA Aqui quiest est une fonction dune ou plu x/19 =0.022 On veut souvent dterminer une quantit une fonction ou plus these variables contributes to theoverall uncer13.69 +0.13 13.55 14 7 0.01 chacune avec sa sa propre propre incertitude. incertitude. Lincertitude Lincertitudede dechacune chacunede deces cesvariab varia chacune avec tainty. We will limit ourselves to give themathlincertitude totale. Nous Nous nous limiterons limiterons donner donner les expressionsmathma mathm lincertitudeematical totale. nous les expressions Moyenne x = 13,56 expressions for 2 in various cases. Fig.13.1A and Table13.1. All data are assumed dans diffrents cas. Les Les quations quations repose surla larelation relation gnrale de fonctio Theequations are based on sur thegeneral relation dans diffrents cas. repose gnrale de lala fonction Dviation standard x = {(xi 13,56)} /18 = 0,095 to have thesame uncertainty/precision. for thefunction: de la moyenne = x/19 = 0,022 =f f( (x, x, y, y, z z)) A= A = f (x, y, z) 13.4. Statistical uncertainties

13.5

13.5. error Propagation

13.74 +0.18 PROPAGATION

13.62

+0.06

DELERREUR LERREUR PROPAGATION DE

des incertitudes statistiques la dviation dviation standardde deAAdpend dpe cas incertitudes statistiques la standard Indes thecase of statistical uncertainties thestandard arise from therandom fluctuations in thenumber deviation of A depends theindependent variindpendantes x,, y y et et z z de la manireon suivante: x de la manire suivante: Les incertitudes statistiques, dfinies dans la Part. 13.2.3, proviennent des fluctuations of events, for instance thenumber of radioactive ables x, y and z as: disintegrations per unit time, rather than from de dsintgrations22 radioactives alatoires du nombre dvnements, par exemple le nombre 22 22 A AA A A A 2 2 22 22 2 2 alimited precision of themeasuring equipment. = + + A + + = par units de temps, plutt que dune prcision limite des instruments de mesure. Pour ces (13.14) xx yy zz A yy zz x x For these statistical fluctuations the theory of fluctuations statistics statistiques la thorie des statistique fournit for une technique mathmatique pour provide themathematical technique theuncertainties are estimated instrumental dcrire la distribution donnes et la dviation standard. Le If rsultat est que la dviation describing des thedata distribution and thestandard sont comme instrumentales, des sim Si les incertitudes incertitudes sont considres considres comme instrumentales, desquations quations s uncertainties, similar equations are to be used for Theresult is thestandard deviation standard de deviation. plusieurs comptages M that dtects durant un intervalle de temps t est simplement : utilises pour lincertitude du rsultat Pour relation gnra calculating theuncertainty thefinal result. Forla pour calculer calculer lincertitudein du rsultatfinal. final. Pour la relation gn of anumber of counts M detected duringtre atime thegeneral relation: interval = M t is simply: (13.11) A A= = f( f(x, x, y, y, z z)) A = f(x, y, z) = M (13.11) Pour un taux de comptage R, i.e. le nombre de coups par seconde, la dviation standard est avec les instrumentales xx , , yyet zz , ,lincertitude AA est :: with theestimated instrumental uncertainties Dx,en avec les incertitudes incertitudes instrumentales et lincertitude en est For thecounting rate R, i.e. thenumber of counts alors: Dy and Dz, theuncertainty in Ais: per second, thestandard deviation then is: 2 2 2 2 A A AA 2 2 R 1 1 2 2 2 2 A A 2 2 2 2 A = x + y + z (13.12) R = M = Rt = A = x y x + (13.12) + z y t t t x z z y Erreurs, et Ajustements Therelative uncertainty of Moyennes thecounting rate is (13.15) Lincertitude relative du taux de comptage est donne par: dbouchant sur quivalentes pour AA et 13.1613 A (Eqs. given by: dbouchantresulting sur les les quations quations quivalentes pourfor et A (Eqs. 13.161 in theequivalent equations DA as exemples a et sont des xxet des R 1 exemples a for et b b sont des coefficients, coefficients, etyysont sont desvariables variablesindpendante indpendant A in theEqs.13.16 13.19. In these exam= (13.13) (13.13) dpendante. ples aand b are constant coefficients, x and y are R dpendante. Rt 250 theindependent variables, Athedependent variable. Il est vident que la prcision relative est meilleure si le taux de comptage est plus lev et le temps de mesure plus long. Le cas des niveaux de confiance lorsquon observe les donnes 149 avec les incertitudes statistiques est similaire celui des incertitudes instrumentales comme nous en avons discut dans la partie prcdente. La probabilit pour quune valeur relle observe sur une priode de temps infinie se situe entre xi + et xi de la valeur mesure

13.4

Dans le Statistical uncertainties,STATISTIQUES defined in Sect.13.2.3, INCERTITUDES

Erreurs, Moyennes et Ajustements Chapitre 13 x2 = 1 / (1/i)2 = 1 / [N(1/i)2] = i2 / N INTRODUCTION Chapitre 13

or

x = i / N

(1) A = ax + by et A = ax by avec les incertitudes x et y; dans les deux cas: fit (1) += by and A= ax byincertitudes with uncertain(1) A = ax A= + by ax et A ax by avec les x et y; 13.6. Least-squares dans les deux cas: 2 ties 2 in both cases: 2 2 and2 ; A = a xx + b yy (13.16) 13.6 AJUSTEMENT PAR LES MOINDRES CARRES Ameasured quantity is often related to some A2 = a2x2 + b2y2 (13.16) other variable, for instance y=f(x). This func2 2 2 Une quantit mesure estany souvent relieas linear, une autre variable, par exempl =aa + b2y2 (13.16) tion may have form such quadratic, A= x/y (2) A = a xy et A x harmonic, arbitrary, et cetera. Thesubject this fonction peut tre de nimporte qu'elle forme, linaire,of quadratique, harmoni (2) A = a xy et A = a x/y (2) A = a xy et2 A = a x/y section is to briefly discuss methods to obtain cetera. Lobjet de cette partie est de discuter brivement des mthod 2 y A2 x themost probable graphical and algebraic adjust2 2 2 = + (13.17) lajustement graphique et algbrique le plus probable dune fonction aux d 2 2 2 y ment of afunction to thedata. x A A x = y+ (13.17) (13.17)Themajor interest 2 2 2 intressant is est lajustement des donnes line droite dun grand theadjustment of astraight to anumber of nombre de d A x y data, which are expected to be linearly related. suppose relies linairement. bx (3) A = a e (3) A = a e bx bx (3) A = a e 13.6.1. Fit to astraight line 13.6.1 AJUSTEMENT LINAIRE /A =x bx (13.18) A/A =A b (13.18) A/A = bx (13.18) fitting is to miniprinciple ofpar least-squares Le principeThe de lajustement les moindres carrs est de minimiser la somm (4) A = a ln( bx) mise thesum of thesquares of thedeviations of (4) A = a ln( bx) dviations des variables dpendantes (y) (lincertitude en x est suppose ng thedependent variable (y) (theuncertainty in x is (4) A = a ln( bx) dune droite prsentant coefficientsfrom a et b : A = a x/x (13.19) assumed to des be negligible) thestraight line A = a x/x (13.19) with coefficients aand b: A = a x/x (13.19) y = a + bx y = a + bx (13.22) 13.5.2. Weighted mean 13.5.2 MOYENNE PONDRE ) la value droite est La dviation de toute valeur from de y (yiany to Thedeviation of donne y(yi) par 13.5.2 Till now, MOYENNE PONDRE when calculating average values, we thestraight line is given by Jusqu prsent a calcul les valeurs moyennes, nous avons considr que tous les havelorsquon considered all numbers to have thesame Jusqu prsent lorsquon a calcul les valeurs moyennes, nous avons considr que tous les yi = ypoids =y a bxi i f(x i affecte precision and thus to have et thesame weight . If we le mme nombres avaient la mme prcision ainsi quils avaient . i)Si on yi mme = yi f( xi) =. ySi a affecte bxi (13.23) poids nombres avaient la mme prcision et ainsi quils avaient le i on assignnombre to each sa number its own standard deviation, chaque chaque propre dviation standard, la moyenne doit alors tre calcule de chaquethemean chaqueis nombre dviation standard, la moyenne doit alors treof calcule de En minimisant la somme de ces dviations on obtient: Minimising thesum these deviations results in: then tosa bepropre calculated according to: la faon suivante: la faon suivante: xi x2i x (13.24) = 0 0 y yii = i x = i 2 (13.20) 1i 2 while applying theabsolute values of Dyi does i x= (13.20) x =12 (13.20) not result into auseful mathematical proceTandis quutiliser les valeurs absolues de yi ne fournit pas une approche ma 1 i 2 dure. Therefore, we are looking for aprocedure i Cest pourquoi, nous recherchons une dmarche pour trouver les coef i2 to find the coefficients aand b, characterising while thestandard deviation of themean is obcaractrisant la laquelle la somme des des dviations: line, by which thesum of carrs thesquares tandis que la dviation standard de lade moyenne est obtenue partir dedroite, : de : par tained from: tandis que la dviation standard la moyenne est obtenue thestraight partir of thedeviations: 1 1 1 1 (yi)2 = (yi a bxi)2 = = 2 2 2 (yi)2 = (yi a bxi)2 (13.25) x 2 i x i est minimise. Les conditions dajustement sont: are: is minimised. Thematching conditions ce qui donne: resulting in: ce qui donne: and ( yi a bxi ) 2 = 0 et 1 1 a x = x = (13.21) (13.21) (13.21) / i(1 )2 / i )2 (1 2 ( y a bxi ) = 0 (13.26) b i Chapitre 13 Le poids de chaque rsultat est inversement proportionnel au carr de la dviation standard; Chapitre 13 Le poids de chaque est inversement proportionnel au carr de la dviation standard; Theweight ofrsultat each result is inversely proportion2 2 2 al to thesquare of thestandard deviation; Theresulting values of aand b are: Les de a et de b obtenues ont: 1/valeurs is le facteur de pondration . . 1/ est est appel le facteur de pondration 1/appel 2 referred to as theweighting factor. xi 2 y x x yi 1 moyenne yii rduit x Si les standard i sont gales, lexpression pour ade la ii2 Sidviations les dviations standard i sont gales, lexpression pour 1 de la x moyenne se rduit xii y = et i se i (13.27a) 2 2 et a = 2 2 2 2 2 If thestandard deviations are equal, theexpresi ii ii ii lEq. lEq. 13.10: 13.10: ii sion for of themean reduces to Eq.13.10: and 252 252 1 1 x2 = 1 / (1/i)2 = 1 / [N(1/i)2] = i2 / N xii y yii x xii y yii 1 1 x b 2 2 2 2 (13.27b) = b= 2 2 2 2 ii ii ii ii or x = i / N tandis tandis que que
150
2 2 2 x x i i x x = i i 22 2 = i 22 ii 2 i ii

1 1

et (13.27a) et de probabilit de Gauss (13.27a) fonction de lEq. 13.5, i.e. de la somme des dviations entre les valeurs y observes (yi) et les valeurs y calcules partir de la relati xi y i xi yi y = f(xi). 1 1 xi2 yi2 (13.27b) b = 1 12 xi y 2i 1 errors, means and fits xi iy xii2 yi i2 1 (13.27b) b= i i 2 2 (13.27b) b = 2 2 2 2 i ii ii ii i tandis que computer programmes. These also exist for comtandis que while tandis que 2 2 posite curves, consisting of thesuperposition of x xi 2 1 2 (13.27c) = 12 xii 2 more than one curve. Even through data points, (13.27c) xi2 2 x xii2 = 1 (13.27c) i 2 i 2 which are not theoretically related to theindepen = 2 2 (13.27c) ii ii ii 2 dent variable, curves can be fitted. One example If thestandard deviations of y are equal, thevalSi les dviations standards de y sont gales, les valeurs de a et de is b sont: thecubic spline. In principle cubic (3rd order) ues of aand b are: Si les dviations standards de y sont gales, les valeurs de a et defits b sont: through successive group of data are adjusted Si les dviations standards de y sont gales, les valeurs de a et de b sont: 2 to each other. Theresulting a = (xi2 y x x y ) / (13.28a)curve can be chosen i i i i a = (xii2 (13.28a) y yii x xii x xiy (13.28a) 2 i) iy i)// to fit all data points, as well as chosen to smooth a = (xi yi xi xiyi) / (13.28a) b = (N xiyi xi yi) / (13.28b) irregularities as much as wanted. b = (N xiyi x xi y yi)) // (13.28b) (13.28b) b = (N x2iiyii xii 2yii) / (13.28b) 2 2 = N x ( x ) (13.28c) = N xii 2 (xii) 2 (13.28c) = N xi2 (xi)2 (13.28c) = N xi (xi) (13.28c) 13.7. Chi-square test Beaucoup de calculateurs de poche rcents ont la possibilit de calculer lajustement des Many modern pocket calculators have theposBeaucoup de calculateurs de poche rcents ont la possibilit The de calculer lajustement des least-squares fit is based on minimising Beaucoupcarrs de calculateurs de Un poche rcents ont la sur possibilit de calculer lajustement des moindres une exemple trouve lafit Fig. 13.3. Les dviations standard sibility ofdroite. calculating the se least-squares moindres carrs une droite. Un exemple se trouve sur la Fig. 13.3. Les dviations standard theexponential of theGaussian to thestraight line. example is shown moindres carrs une droite. Un An exemple se trouve sur lain Fig. 13.3. Les dviations standard probability funcdes coefficients aet b sont: tion of Eq.13.5, i.e. of thesum of the(quadratic) Fig.13.3. des coefficients a et b The sont:standard deviations of the coeffides coefficients a et b sont:2 Fig. 13.3. Ajustement linaire des moindres carrs sur de nombreuses donnes (x,y), deviations between theobserved y values (yi) and cients aand b are: x 1 les variables et dpendantes relies par lquation a = 1 xii 2 (13.29a) they values indpendantes calculated from therelation sont between 2 xi 2 1 a = (13.29a) Toutes valeurs la mme prcision. y and xles : y=f( xi).y ont(13.29a) a = 2 (13.29a) ii et For the straight line fit this comes to calcuet lating coefficients of the linear les relation and et Pour lajustement the linaire ceci revient calculer coefficients de la r 1 1 a bxi)2 is y=a+ bx for which thesum S ( y i 2 (13.29b) b = 1 12 y = a + bx pour laquelle la somme (yi a bxi) est minimale (Eq. 13.25). En 1 1 minimal (Eq.13.25).(13.29b) In view of thedefinition of b = i2 (13.29b) b = (13.29b) il est logique de thesame prendre la mme somme t log dfinition de la probabilit, P 2 i, it i , logical to take sum theprobability, P i i same sum of the squaredeviations deviationsin en relation avec la dviation standard of thesquare relation to thestandard 13.6.2 AJUSTEMENT NON LINAIRE as ameasure for the of fit: deviation asdeviation a measure for the goodness of goodness fit: 13.6.2 AJUSTEMENT NON LINAIRE 13.6.2. Fit to non-linear curves 13.6.2 AJUSTEMENT NON LINAIRE Lajustement des moindres carrs, par exemple, les courbes quadratiques ou polynomiales de 2 N ou yi a bxi Lajustement desleast-squares moindres carrs, par exemple, lesquadratic courbes quadratiques polynomiales de 2 The fit to, for instance, = quantitativement. Lajustement moindres carrs, par exemple, courbes de (13.30) second degr,des exponentielles et arbitraires, ne les seront pas quadratiques traites ou polynomiales Elles or second-degree polynomial, harmonic, expo second degr, exponentielles et arbitraires, ne seront pas traites quantitativement. Elles i =1 i Elles second degr, exponentielles et curves arbitraires, pas normale traites quantitativement. peuvent tre calcules analytiquement, maisne la seront dmarche consiste utiliser les nential and arbitrary will treated peuvent tre calcules analytiquement, maisnot la be dmarche normale consiste utiliser les peuvent tre calcules analytiquement, mais la dmarche normale consiste utiliser les programmes informatiques appropris. existent galement pour les courbes combines, For theset of in Fig. 13.3 and Table 13.2 Pour le jeu de donnes de ladata Fig. 13.3 et du Tableau 13.2 le 2 est calcul. quantitatively. These can beIls calculated analytiprogrammes informatiques appropris. Ils existent galement the pour courbes combines, cally, but thenormal is to courbe. apply theproper 2 les is calculated. programmes informatiques appropris. Ils existent galement pour les courbes combines, consistant en la superposition deroutine plus dune Mme partir des points, qui ne sont pas En rsum lajustement aux donnes est celui qui minimise 2. L consistant en la superposition de plus dune courbe. Mme partir des points,optimum qui ne sont pas consistant en la superposition de plus dune courbe. Mme partir destre points, qui ne sont pas relis thoriquement une variable indpendante, les courbes peuvent ajustes. Le spline 2 de minimiser est la Le mthode relis thoriquement une variable indpendante, lespermet courbes peuvent tre ajustes. spline des moindres carrs. Le rsultat du relis thoriquement une variable indpendante, les courbes peuvent tre ajustes. spline cubique en est un exemple. En principe les ajustements cubiques (3me ordre) Le partir de 2 rassurant si le divis par le nombre cubiques (3me ordre) partir de de donnes (=19) moins le degr d cubique en est un exemple. En principe les ajustements cubique successifs en est un de exemple. Ensont principe les ajustements cubiques (3mersultante ordre) peut partirtre de groupes donnes, ajusts les uns aux autres. La courbe nombre de La paramtres dterminer, ici = 1) est environ gal un (dans ce cas groupes successifs de donnes, sont ajusts les uns aux autres. courbe rsultante peut tre groupespour successifs donnes, sont ajusts les unslisser aux autres. La courbe rsultante peut tre choisie ajusterde tous les points, ou choisie pour les irrgularits autant que dsir. choisie pour ajuster tous les points, ou choisie pour lisser les irrgularits autant que dsir. choisie pour ajuster tous les points, ou choisie pour lisser les irrgularits autant que dsir.
i i

xi 2 1 a= i 2 a = i2 i

i2 i i2 i2 i

2 xiii2 2

xy
i 2i i i 2i i2 i

254 254 254

Fig. 13.3. Linear least-squares fit through anumber of (x,y) data sets, of which theindependent and dependent variables are related by theequation y=2.5 + 0.5x. All y values have thesame precision.

151

INTRODUCTION

TABLE 12.2. Series of (xi, yi) data sets obeying therelation y=a+ bx, resulting in avalue of c2.
x 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 2 yi 2.9 0.8 2.4 0.8 4.1 0.8 5.7 0.8 5.7 0.8 4.6 0.8 7.3 0.8 4.9 0.8 7.0 0.8 7.1 0.8 7.5 0.8 9.2 0.8 8.6 0.8 9.4 0.8 8.9 0.8 11.1 0.8 12.8 0.8 12.4 0.8 10.9 0.8 y=2.5 + 0.5xi 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 [y f(xi)]2/2 0.016 1.891 0.016 2.250 0.766 1.266 2.641 4.000 0.000 0.250 0.391 0.766 0.250 0.016 1.891 0.563 5.063 1.266 1.891 12.094

In summary, theoptimum fit to data is that which minimises 2. Themethod by which 2 is minimised is theleast-squares method. Theresult of a2 test is reassuring, if the2 divided by thenumber of data (=19) minus thedegrees of freedom (=thenumber of parameters to be determined, here=1) is about equal to one (in this case=12/18).

Note: Thegraph for these data is shown in Fig.13.3. Theoptimum fit to thedata is that which minimises 2.

152

Symbols and units

a [CO2aq] = concentration dissolved CO2 a year y a activity ratio (y mass number, e.g. 14 a) aq dissolved A (atomic) mass number A absolute (radio)activity (e.g. 14A) AMS accelerator mass spectrometer l/v fractionation factor (l rel. to v) k kinetic fractionation factor alpha particle b [HCO!] = concentration dissolved bicarbonate B magnetic field B background counting rate Bq Becquerel = 1 disintegrations-1 b beta particle 2 c [CO 3 ] = concentration dissolved carbonate ions 0 C degree centigrade CT concentration dissolved inorganic carbon C3 Calvin photosynthesis C4 Hatch-Slack photosynthesis CAM Crassulacean Acid Metabolism Ci Curie = 3.7 1010 dps Cl chlorinity (in g of chloride per kg of water = ) d deuterium excess of MWL d day = 8.6400 105 s dpm disintegrations per minute dps disintegrations per second D diffusion constant/coefficient DIC dissolved inorganic carbon DOC dissolved organic carbon x relative isotope ratio (e.g. 13) (defined from xR) y relative activity ratio (e.g. 14) (defined from yA or ya) E energy EB binding energy EC electron conversion fractionation (constant) (enrichment/ depletion) k kinetic fractionation (constant) f fraction F force g gram GM Geiger Mller counter g gamma particle/radiation h relative humidity h hour I electric current IAEA International Atomic Energy Agency IRMS isotope ratio mass spectrometer J Joule keV kiloelectronvolt = 103 eV K equilibrium/acidity constant K degree Kelvin LSS liquid scintillation spectrometer l (radioactive) decay constant m mass m meter min minute mol symbol for mole mole number of grams equal to molar weight M molar weight, mole MeV millionelectronvolt = 106 eV MS mass spectrometer MWL meteoric water line m reduced mass n neutron N neutron number N amount NBS National Bureau of Standards NIST National Institute of Standards and Technology, USA n neutrino n frequency Ox oxalic acid (14C standard) p pressure p proton pH = -10log [H+] pCi picoCurie = 10-12 Ci pMC percent Modern Carbon P probability PDB PeeDee Belemnite PGC proportional gas counter q partition function q electric charge Q nuclear reaction energy r radius x R isotope ratio (x mass number, e.g. 13 R) s second s slope of MWL = 8

153

sp spallation S salinity (in g of salt per kg of water = ) SLAP standard light Antarctic precipitation SMOW standard mean ocean water STP standard temperature and pressure (0oC, 1 atm) s standard deviation S total inorganic carbon
concentration = CT t time t temperature (in oC) T absolute temperature (in K) T1/2 half-life TU tritium unit [3H]/[1H] = 10-18 = 0.118 Bq/L q exponent in fractionation factor ratio for (DM=2)/(DM=1) t mean life v velocity V volume V volt VPDB Vienna-PDB VSMOW Vienna-SMOW Z atomic number

154

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